Higher density polyolefins with improved stress crack resistance

ABSTRACT

Disclosed herein are polymerization processes for the production of olefin polymers. These polymerization processes can employ a catalyst system containing two or three metallocene components, resulting in ethylene-based copolymers that can have a medium density and improved stress crack resistance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 14/842,888, filed on Sep. 2, 2015, now U.S. Pat.No. 9,394,393, which is a continuation application of U.S. patentapplication Ser. No. 14/018,455, filed on Sep. 5, 2013, now U.S. Pat.No. 9,156,970, the disclosures of which are incorporated herein byreference in their entirety.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.Chromium-based catalyst systems can, for example, produce olefinpolymers having good extrusion processibility and polymer melt strength,typically due to their broad molecular weight distribution (MWD).

In some end-use applications, it can be beneficial to have theprocessibility and melt strength similar to that of an olefin polymerproduced from a chromium-based catalyst system, as well as improvementsin stress crack resistance (e.g., higher notched tensiles, lower naturaldraw ratios) at equal or higher polymer densities. Accordingly, it is tothese ends that the present invention is directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to new catalyst compositions,methods for preparing catalyst compositions, methods for using thecatalyst compositions to polymerize olefins, the polymer resins producedusing such catalyst compositions, and articles produced using thesepolymer resins. In particular, aspects of the present invention aredirected to catalyst compositions employing two or three metallocenecatalyst components. The first catalyst component can comprise anunbridged zirconium or hafnium based metallocene compound, while thesecond catalyst component can comprise a bridged zirconium or hafniumbased metallocene compound with a fluorenyl group. If used, the thirdcatalyst component can comprise a titanium or chromium half-metallocenecompound. Such catalyst compositions can be used to produce, forexample, ethylene-based copolymers having medium densities and improvedstress crack resistance.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer under polymerization conditions to produce an olefin polymer.Generally, the catalyst composition employed can comprise any of thecatalyst component I metallocene compounds, any of the catalystcomponent II metallocene compounds, any of the optional catalystcomponent III metallocene compounds, and any of the activators andoptional co-catalysts disclosed herein. For example, organoaluminumcompounds can be utilized in the catalyst compositions and/orpolymerization processes.

Polymers produced from the polymerization of olefins, resulting inhomopolymers, copolymers, terpolymers, etc., can be used to producevarious articles of manufacture. A representative and non-limitingexample of an olefin polymer (e.g., an ethylene copolymer) consistentwith aspects of this invention can be characterized as having thefollowing properties: a density from about 0.930 to about 0.948 g/cm³, azero-shear viscosity greater than about 5×10⁵ Pa-sec, a CY-a parameterin a range from about 0.01 to about 0.40, a peak molecular weight in arange from about 30,000 to about 130,000 g/mol, and a reverse comonomerdistribution. Another representative and non-limiting ethylene-basedpolymer described herein can have a density from about 0.930 to about0.948 g/cm³, a single point notched constant tensile load of at least6,500 hours, and a natural draw ratio of less than or equal to about525%. Yet another representative and non-limiting ethylene-based polymerdescribed herein can have a density from about 0.930 to about 0.948g/cm³, and a relationship between natural draw ratio (NDR, %) anddensity (g/cm³) defined by the equation, NDR<7800(density)−6800 or,additionally or alternatively, NDR<13404(density)−12050.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects andembodiments may be directed to various feature combinations andsub-combinations described in the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 4.

FIG. 2 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 10.

FIG. 3 presents a plot of the molecular weight distribution and shortchain branch distribution of the polymer of Example 12.

FIG. 4 presents a dynamic rheology plot (viscosity versus frequency) at190° C. for the polymers of Examples 1 and 7.

FIG. 5 presents a dynamic rheology plot (viscosity versus frequency) at190° C. for the polymers of Examples 1 and 9.

FIG. 6 presents a dynamic rheology plot (viscosity versus frequency) at190° C. for the polymers of Examples 1 and 10.

FIG. 7 presents a dynamic rheology plot (viscosity versus frequency) at190° C. for the polymers of Examples 13 and 14.

FIG. 8 presents a dynamic rheology plot (viscosity versus frequency) at190° C. for the polymers of Examples 18 and 21.

FIG. 9 presents a plot of the molecular weight distributions of thepolymers of Examples 1 and 7.

FIG. 10 presents a plot of the molecular weight distributions of thepolymers of Examples 1 and 10.

FIG. 11 presents a plot of the molecular weight distributions of thepolymers of Examples 13 and 14.

FIG. 12 presents a plot of the molecular weight distributions of thepolymers of Examples 18 and 21.

FIG. 13 presents a plot of the molecular weight distributions of thepolymers of Examples 4 and 23-25.

FIG. 14 presents a plot of the natural draw ratio versus the density forcertain polymers described in the Examples.

FIG. 15 presents a plot of the natural draw ratio versus the density forcertain polymers described in the Examples.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a catalyst compositionconsistent with aspects of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; (i) catalyst component I, (ii) catalyst component II, (iii) anactivator, and (iv) optionally, a co-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a metallocenecompound” is meant to encompass one, or mixtures or combinations of morethan one, activator-support or metallocene compound, respectively,unless otherwise specified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane, while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that can arisefrom a particular set of substituents.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Unless otherwise specified, “substituted” is intended to be non-limitingand include inorganic substituents or organic substituents as understoodby one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon (that is, agroup containing only carbon and hydrogen). Non-limiting examples ofhydrocarbyl groups include alkyl, alkenyl, aryl, and aralkyl groups,amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer can be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process can involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to an activator-support. The term“co-catalyst” is used regardless of the actual function of the compoundor any chemical mechanism by which the compound may operate.

The terms “chemically-treated solid oxide,” “treated solid oxidecompound,” and the like, are used herein to indicate a solid, inorganicoxide of relatively high porosity, which can exhibit Lewis acidic orBrønsted acidic behavior, and which has been treated with anelectron-withdrawing component, typically an anion, and which iscalcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The “activator-support” of thepresent invention can be a chemically-treated solid oxide. The terms“support” and “activator-support” are not used to imply these componentsare inert, and such components should not be construed as an inertcomponent of the catalyst composition. The term “activator,” as usedherein, refers generally to a substance that is capable of converting ametallocene component into a catalyst that can polymerize olefins, orconverting a contact product of a metallocene component and a componentthat provides an activatable ligand (e.g., an alkyl, a hydride) to themetallocene, when the metallocene compound does not already comprisesuch a ligand, into a catalyst that can polymerize olefins. This term isused regardless of the actual activating mechanism. Illustrativeactivators include activator-supports, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.Aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds generally are referred to as activators if used in a catalystcomposition in which an activator-support is not present. If thecatalyst composition contains an activator-support, then thealuminoxane, organoboron or organoborate, and ionizing ionic materialsare typically referred to as co-catalysts.

The term “metallocene” as used herein describes compounds comprising atleast one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands may include H, therefore this inventioncomprises ligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like. In some contexts, themetallocene is referred to simply as the “catalyst,” in much the sameway the term “co-catalyst” is used herein to refer to, for example, anorganoaluminum compound.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic site, or the fate of the co-catalyst, themetallocene compound(s), any olefin monomer used to prepare aprecontacted mixture, or the activator (e.g., activator-support), aftercombining these components. Therefore, the terms “catalyst composition,”“catalyst mixture,” “catalyst system,” and the like, encompass theinitial starting components of the composition, as well as whateverproduct(s) may result from contacting these initial starting components,and this is inclusive of both heterogeneous and homogenous catalystsystems or compositions. The terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, can be used interchangeablythroughout this disclosure.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another. Similarly, the term“contacting” is used herein to refer to materials which can be blended,mixed, slurried, dissolved, reacted, treated, or otherwise contacted insome other manner.

The term “precontacted” mixture is used herein to describe a firstmixture of catalyst components that are contacted for a first period oftime prior to the first mixture being used to form a “postcontacted” orsecond mixture of catalyst components that are contacted for a secondperiod of time. Typically, the precontacted mixture can describe amixture of a metallocene compound (one or more than one), olefin monomer(or monomers), and organoaluminum compound (or compounds), before thismixture is contacted with an activator-support(s) and optionaladditional organoaluminum compound. Thus, precontacted describescomponents that are used to contact each other, but prior to contactingthe components in the second, postcontacted mixture. Accordingly, thisinvention can occasionally distinguish between a component used toprepare the precontacted mixture and that component after the mixturehas been prepared. For example, according to this description, it ispossible for the precontacted organoaluminum compound, once it iscontacted with the metallocene compound and the olefin monomer, to havereacted to form at least one chemical compound, formulation, orstructure different from the distinct organoaluminum compound used toprepare the precontacted mixture. In this case, the precontactedorganoaluminum compound or component is described as comprising anorganoaluminum compound that was used to prepare the precontactedmixture.

Additionally, the precontacted mixture can describe a mixture ofmetallocene compound(s) and organoaluminum compound(s), prior tocontacting this mixture with an activator-support(s). This precontactedmixture also can describe a mixture of metallocene compound(s), olefinmonomer(s), and activator-support(s), before this mixture is contactedwith an organoaluminum co-catalyst compound or compounds.

Similarly, the term “postcontacted” mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the “precontacted” orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term “postcontacted” mixture is usedherein to describe the mixture of metallocene compound(s), olefinmonomer(s), organoaluminum compound(s), and activator-support(s) formedfrom contacting the precontacted mixture of a portion of thesecomponents with any additional components added to make up thepostcontacted mixture.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language, a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can have 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, aswell as any range between these two numbers (for example, a C₁ to C₈hydrocarbyl group), and also including any combination of ranges betweenthese two numbers (for example, a C₂ to C₄ and a C₁₂ to C₁₆ hydrocarbylgroup).

Similarly, another representative example follows for the peak molecularweight (Mp) of an olefin polymer produced in an aspect of thisinvention. By a disclosure that the Mp can be in a range from about30,000 to about 130,000 g/mol, Applicants intend to recite that the Mpcan be any molecular weight in the range and, for example, can be equalto about 30,000, about 40,000, about 50,000, about 60,000, about 70,000,about 80,000, about 90,000, about 100,000, about 110,000, about 120,000,or about 130,000 g/mol. Additionally, the Mp can be within any rangefrom about 30,000 to about 130,000 (for example, from about 40,000 toabout 80,000), and this also includes any combination of ranges betweenabout 30,000 and about 130,000 (for example, the Mp can be in a rangefrom about 30,000 to about 75,000, or from about 90,000 to about125,000). Likewise, all other ranges disclosed herein should beinterpreted in a manner similar to these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to new catalystcompositions, methods for preparing catalyst compositions, methods forusing the catalyst compositions to polymerize olefins, the polymerresins produced using such catalyst compositions, and articles producedusing these polymer resins. In particular, the present invention relatesto catalyst compositions containing two or more metallocene components,to polymerization processes utilizing such catalyst compositions, and tothe resulting olefin polymers produced from the polymerizationprocesses.

Catalyst Component I

Catalyst component I can comprise an unbridged zirconium or hafniumbased metallocene compound and/or an unbridged zirconium and/or hafniumbased dinuclear metallocene compound. In one aspect, for instance,catalyst component I can comprise an unbridged zirconium or hafniumbased metallocene compound containing two cyclopentadienyl groups, twoindenyl groups, or a cyclopentadienyl and an indenyl group. In anotheraspect, catalyst component I can comprise an unbridged zirconium orhafnium based metallocene compound containing two cyclopentadienylgroups. In yet another aspect, catalyst component I can comprise anunbridged zirconium or hafnium based metallocene compound containing twoindenyl groups. In still another aspect, catalyst component I cancomprise an unbridged zirconium or hafnium based metallocene compoundcontaining a cyclopentadienyl and an indenyl group.

In some aspects, catalyst component I can comprise an unbridgedzirconium based metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group,while in other aspects, catalyst component I can comprise a dinuclearunbridged metallocene compound with an alkenyl linking group.

Catalyst component I can comprise, in particular aspects of thisinvention, an unbridged metallocene compound having formula (I):

Within formula (I), M, Cp^(A), Cp^(B), and each X are independentelements of the unbridged metallocene compound. Accordingly, theunbridged metallocene compound having formula (I) can be described usingany combination of M, Cp^(A), Cp^(B), and X disclosed herein.

Unless otherwise specified, formula (I) above, any other structuralformulas disclosed herein, and any metallocene complex, compound, orspecies disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display cis or trans isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures.

In accordance with aspects of this invention, the metal in formula (I),M, can be Ti, Zr, or Hf. In one aspect, for instance, M can be Zr or Hf,while in another aspect, M can be Ti; alternatively, M can be Zr; oralternatively, M can be Hf.

Each X in formula (I) independently can be a monoanionic ligand. In someaspects, suitable monoanionic ligands can include, but are not limitedto, H (hydride), BH₄, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ to C₃₆hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group, —OBR¹₂, or —OSO₂R¹, wherein R¹ is a C₁ to C₃₆ hydrocarbyl group. It iscontemplated that each X can be either the same or a differentmonoanionic ligand.

In one aspect, each X independently can be H, BH₄, a halide (e.g., F,Cl, Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈ hydrocarboxygroup, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈ hydrocarbylsilylgroup, or a C₁ to C₁₈ hydrocarbylaminylsilyl group. Alternatively, eachX independently can be H, BH₄, a halide, OBR¹ ₂, or OSO₂R¹, wherein R¹is a C₁ to C₁₈ hydrocarbyl group. In another aspect, each Xindependently can be H, BH₄, a halide, a C₁ to C₁₂ hydrocarbyl group, aC₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂ hydrocarbylaminyl group, a C₁to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂ hydrocarbylaminylsilyl group,OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ to C₁₂ hydrocarbyl group. Inanother aspect, each X independently can be H, BH₄, a halide, a C₁ toC₁₀ hydrocarbyl group, a C₁ to C₁₀ hydrocarboxy group, a C₁ to C₁₀hydrocarbylaminyl group, a C₁ to C₁₀ hydrocarbylsilyl group, a C₁ to C₁₀hydrocarbylaminylsilyl group, OBR¹ ₂, or OSO₂R¹, wherein R¹ is a C₁ toC₁₀ hydrocarbyl group. In yet another aspect, each X independently canbe H, BH₄, a halide, a C₁ to C₈ hydrocarbyl group, a C₁ to C₈hydrocarboxy group, a C₁ to C₈ hydrocarbylaminyl group, a C₁ to C₈hydrocarbylsilyl group, a C₁ to C₈ hydrocarbylaminylsilyl group, OBR¹ ₂,or OSO₂R¹, wherein R¹ is a C₁ to C₈ hydrocarbyl group. In still anotheraspect, each X independently can be a halide or a C₁ to C₁₈ hydrocarbylgroup. For example, each X can be Cl.

The hydrocarbyl group which can be an X in formula (I) can be a C₁ toC₃₆ hydrocarbyl group, including, but not limited to, a C₁ to C₃₆ alkylgroup, a C₂ to C₃₆ alkenyl group, a C₄ to C₃₆ cycloalkyl group, a C₆ toC₃₆ aryl group, or a C₇ to C₃₆ aralkyl group. For instance, each Xindependently can be a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group,a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈aralkyl group; alternatively, each X independently can be a C₁ to C₁₂alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂ cycloalkyl group, aC₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group; alternatively, eachX independently can be a C₁ to C₁₀ alkyl group, a C₂ to C₁₀ alkenylgroup, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ aryl group, or a C₇ toC₁₀ aralkyl group; or alternatively, each X independently can be a C₁ toC₅ alkyl group, a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, aC₆ to C₈ aryl group, or a C₇ to C₈ aralkyl group.

Accordingly, in some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In some aspects, the alkyl group which can be an X informula (I) can be a methyl group, an ethyl group, a n-propyl group, aniso-propyl group, a n-butyl group, an iso-butyl group, a sec-butylgroup, a tert-butyl group, a n-pentyl group, an iso-pentyl group, asec-pentyl group, or a neopentyl group; alternatively, a methyl group,an ethyl group, an iso-propyl group, a tert-butyl group, or a neopentylgroup; alternatively, a methyl group; alternatively, an ethyl group;alternatively, a n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.

Suitable alkenyl groups which can be an X in formula (I) can include,but are not limited to, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a undecenyl group, a dodecenylgroup, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, ahexadecenyl group, a heptadecenyl group, or an octadecenyl group. Suchalkenyl groups can be linear or branched, and the double bond can belocated anywhere in the chain. In one aspect, each X in formula (I)independently can be an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, or a decenyl group, while in another aspect,each X in formula (I) independently can be an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, or a hexenyl group. Forexample, an X can be an ethenyl group; alternatively, a propenyl group;alternatively, a butenyl group; alternatively, a pentenyl group; oralternatively, a hexenyl group. In yet another aspect, an X can be aterminal alkenyl group, such as a C₃ to C₁₈ terminal alkenyl group, a C₃to C₁₂ terminal alkenyl group, or a C₃ to C₈ terminal alkenyl group.Illustrative terminal alkenyl groups can include, but are not limitedto, a prop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-ylgroup, a hex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-ylgroup, a non-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.

Each X in formula (I) can be a cycloalkyl group, including, but notlimited to, a cyclobutyl group, a substituted cyclobutyl group, acyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group,a substituted cyclohexyl group, a cycloheptyl group, a substitutedcycloheptyl group, a cyclooctyl group, or a substituted cyclooctylgroup. For example, an X in formula (I) can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. Moreover, each X in formula (I) independently can be acyclobutyl group or a substituted cyclobutyl group; alternatively, acyclopentyl group or a substituted cyclopentyl group; alternatively, acyclohexyl group or a substituted cyclohexyl group; alternatively, acycloheptyl group or a substituted cycloheptyl group; alternatively, acyclooctyl group or a substituted cyclooctyl group; alternatively, acyclopentyl group; alternatively, a substituted cyclopentyl group;alternatively, a cyclohexyl group; or alternatively, a substitutedcyclohexyl group. Substituents which can be utilized for the substitutedcycloalkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted cycloalkyl groupwhich can be an X in formula (I).

In some aspects, the aryl group which can be an X in formula (I) can bea phenyl group, a substituted phenyl group, a naphthyl group, or asubstituted naphthyl group. In an aspect, the aryl group can be a phenylgroup or a substituted phenyl group; alternatively, a naphthyl group ora substituted naphthyl group; alternatively, a phenyl group or anaphthyl group; alternatively, a substituted phenyl group or asubstituted naphthyl group; alternatively, a phenyl group; oralternatively, a naphthyl group. Substituents which can be utilized forthe substituted phenyl groups or substituted naphthyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted phenyl groups or substituted naphthylgroups which can be an X in formula (I).

In an aspect, the substituted phenyl group which can be an X in formula(I) can be a 2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other aspects, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe an X group(s) in formula (I).

In some aspects, the aralkyl group which can be an X group in formula(I) can be a benzyl group or a substituted benzyl group. In an aspect,the aralkyl group can be a benzyl group or, alternatively, a substitutedbenzyl group. Substituents which can be utilized for the substitutedaralkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted aralkyl groupwhich can be an X group(s) in formula (I).

In an aspect, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be an X in formula (I) independently can be a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. Specific hydrocarbyl groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents of the substitutedcycloalkyl groups, substituted aryl groups, or substituted aralkylgroups which can be an X in formula (I). For instance, the hydrocarbylsubstituent can be an alkyl group, such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, a n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, -(alkyl, aryl, oraralkyl)-O-(alkyl, aryl, or aralkyl) groups, and —O(CO)-(hydrogen orhydrocarbyl) groups, and these groups can comprise up to about 36 carbonatoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxygroups). Illustrative and non-limiting examples of hydrocarboxy groupswhich can be an X in formula (I) can include, but are not limited to, amethoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxygroup, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, a neo-pentoxy group, a phenoxy group,a toloxy group, a xyloxy group, a 2,4,6-trimethylphenoxy group, abenzoxy group, an acetylacetonate group (acac), a formate group, anacetate group, a stearate group, an oleate group, a benzoate group, andthe like. In an aspect, the hydrocarboxy group which can be an X informula (I) can be a methoxy group; alternatively, an ethoxy group;alternatively, an n-propoxy group; alternatively, an isopropoxy group;alternatively, an n-butoxy group; alternatively, a sec-butoxy group;alternatively, an isobutoxy group; alternatively, a tert-butoxy group;alternatively, an n-pentoxy group; alternatively, a 2-pentoxy group;alternatively, a 3-pentoxy group; alternatively, a 2-methyl-1-butoxygroup; alternatively, a tert-pentoxy group; alternatively, a3-methyl-1-butoxy group, alternatively, a 3-methyl-2-butoxy group;alternatively, a neo-pentoxy group; alternatively, a phenoxy group;alternatively, a toloxy group; alternatively, a xyloxy group;alternatively, a 2,4,6-trimethylphenoxy group; alternatively, a benzoxygroup; alternatively, an acetylacetonate group; alternatively, a formategroup; alternatively, an acetate group; alternatively, a stearate group;alternatively, an oleate group; or alternatively, a benzoate group.

The term hydrocarbylaminyl group is used generically herein to refercollectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl,dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, oraralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwisespecified, the hydrocarbylaminyl groups which can be an X in formula (I)can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁to C₁₀, or C₁ to C₈ hydrocarbylaminyl groups). Accordingly,hydrocarbylaminyl is intended to cover both (mono)hydrocarbylaminyl anddihydrocarbylaminyl groups. In some aspects, the hydrocarbylaminyl groupwhich can be an X in formula (I) can be, for instance, a methylaminylgroup (—NHCH₃), an ethylaminyl group (—NHCH₂CH₃), an n-propylaminylgroup (—NHCH₂CH₂CH₃), an iso-propylaminyl group (—NHCH(CH₃)₂), ann-butylaminyl group (—NHCH₂CH₂CH₂CH₃), a t-butylaminyl group(—NHC(CH₃)₃), an n-pentylaminyl group (—NHCH₂CH₂CH₂CH₂CH₃), aneo-pentylaminyl group (—NHCH₂C(CH₃)₃), a phenylaminyl group (—NHC₆H₅),a tolylaminyl group (—NHC₆H₄CH₃), or a xylylaminyl group(—NHC₆H₃(CH₃)₂); alternatively, a methylaminyl group; alternatively, anethylaminyl group; alternatively, a propylaminyl group; oralternatively, a phenylaminyl group. In other aspects, thehydrocarbylaminyl group which can be an X in formula (I) can be, forinstance, a dimethylaminyl group (—N(CH₃)₂), a diethylaminyl group(—N(CH₂CH₃)₂), a di-n-propylaminyl group (—N(CH₂CH₂CH₃)₂), adi-iso-propylaminyl group (—N(CH(CH₃)₂)₂), a di-n-butylaminyl group(—N(CH₂CH₂CH₂CH₃)₂), a di-t-butylaminyl group (—N(C(CH₃)₃)₂), adi-n-pentylaminyl group (—N(CH₂CH₂CH₂CH₂CH₃)₂), a di-neo-pentylaminylgroup (—N(CH₂C(CH₃)₃)₂), a di-phenylaminyl group (—N(C₆H₅)₂), adi-tolylaminyl group (—N(C₆H₄CH₃)₂), or a di-xylylaminyl group(—N(C₆H₃(CH₃)₂)₂); alternatively, a dimethylaminyl group; alternatively,a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; oralternatively, a di-phenylaminyl group.

In accordance with some aspects disclosed herein, each X independentlycan be a C₁ to C₃₆ hydrocarbylsilyl group; alternatively, a C₁ to C₂₄hydrocarbylsilyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₈ hydrocarbylsilyl group. In anaspect, each hydrocarbyl (one or more) of the hydrocarbylsilyl group canbe any hydrocarbyl group disclosed herein (e.g., a C₁ to C₅ alkyl group,a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ arylgroup, a C₇ to C₈ aralkyl group, etc.). As used herein, hydrocarbylsilylis intended to cover (mono)hydrocarbylsilyl (—SiH₂R), dihydrocarbylsilyl(—SiHR₂), and trihydrocarbylsilyl (—SiR₃) groups, with R being ahydrocarbyl group. In one aspect, the hydrocarbylsilyl group can be a C₃to C₃₆ or a C₃ to C₁₈ trihydrocarbylsilyl group, such as, for example, atrialkylsilyl group or a triphenylsilyl group. Illustrative andnon-limiting examples of hydrocarbylsilyl groups which can be an Xgroup(s) in formula (I) can include, but are not limited to,trimethylsilyl, triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl),tributylsilyl, tripentylsilyl, triphenylsilyl, allyl dimethylsilyl, andthe like.

A hydrocarbylaminylsilyl group is used herein to refer to groupscontaining at least one hydrocarbon moiety, at least one N atom, and atleast one Si atom. Illustrative and non-limiting examples ofhydrocarbylaminylsilyl groups which can be an X can include, but are notlimited to —N(SiMe₃)₂, —N(SiEt₃)₂, and the like. Unless otherwisespecified, the hydrocarbylaminylsilyl groups which can be X can compriseup to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₂, orC₁ to C₈ hydrocarbylaminylsilyl groups). In an aspect, each hydrocarbyl(one or more) of the hydrocarbylaminylsilyl group can be any hydrocarbylgroup disclosed herein (e.g., a C₁ to C₅ alkyl group, a C₂ to C₅ alkenylgroup, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, a C₇ to C₈aralkyl group, etc.). Moreover, hydrocarbylaminylsilyl is intended tocover —NH(SiH₂R), —NH(SiHR₂), —NH(SiR₃), —N(SiH₂R)₂, —N(SiHR₂)₂, and—N(SiR₃)₂ groups, among others, with R being a hydrocarbyl group.

In an aspect, each X independently can be —OBR¹ ₂ or —OSO₂R¹, wherein R¹is a C₁ to C₃₆ hydrocarbyl group, or alternatively, a C₁ to C₁₈hydrocarbyl group. The hydrocarbyl group in OBR¹ ₂ and/or OSO₂R¹independently can be any hydrocarbyl group disclosed herein, such as,for instance, a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₄to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈ aralkylgroup; alternatively, a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenylgroup, a C₄ to C₁₂ cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ toC₁₂ aralkyl group; or alternatively, a C₁ to C₈ alkyl group, a C₂ to C₈alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or aC₇ to C₈ aralkyl group.

In one aspect, each X independently can be H, BH₄, a halide, or a C₁ toC₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother aspect, each X independently can be H, BH₄, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another aspect, each Xindependently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another aspect, each X can be H;alternatively, F; alternatively, Cl; alternatively, Br; alternatively,I; alternatively, BH₄; alternatively, a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, a C₁ toC₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₁₈ hydrocarbylaminylsilyl group.

Each X independently can be, in some aspects, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, formate,acetate, stearate, oleate, benzoate, an alkylaminyl, a dialkylaminyl, atrihydrocarbylsilyl, or a hydrocarbylaminylsilyl; alternatively, H, ahalide, methyl, phenyl, or benzyl; alternatively, an alkoxy, an aryloxy,or acetylacetonate; alternatively, an alkylaminyl or a dialkylaminyl;alternatively, a trihydrocarbylsilyl or hydrocarbylaminylsilyl;alternatively, H or a halide; alternatively, methyl, phenyl, benzyl, analkoxy, an aryloxy, acetylacetonate, an alkylaminyl, or a dialkylaminyl;alternatively, H; alternatively, a halide; alternatively, methyl;alternatively, phenyl; alternatively, benzyl; alternatively, an alkoxy;alternatively, an aryloxy; alternatively, acetylacetonate;alternatively, an alkylaminyl; alternatively, a dialkylaminyl;alternatively, a trihydrocarbylsilyl; or alternatively, ahydrocarbylaminylsilyl. In these and other aspects, the alkoxy, aryloxy,alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C₃₆, a C₁ to C₁₈, a C₁ to C₁₂, ora C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, each X independently can be, in certain aspects, a halide or aC₁ to C₁₈ hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, or hydrocarbylaminyl silyl group; or alternatively, methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In formula (I), Cp^(A) and Cp^(B) independently can be a substituted orunsubstituted cyclopentadienyl or indenyl group. In one aspect, Cp^(A)and Cp^(B) independently can be an unsubstituted cyclopentadienyl orindenyl group. Alternatively, Cp^(A) and Cp^(B) independently can be asubstituted indenyl or cyclopentadienyl group, for example, having up to5 substituents.

If present, each substituent on Cp^(A) and Cp^(B) independently can beH, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group. Importantly, each substituent on Cp^(A) and/orCp^(B) can be either the same or a different substituent group.Moreover, each substituent can be at any position on the respectivecyclopentadienyl or indenyl ring structure that conforms with the rulesof chemical valence. In an aspect, the number of substituents on Cp^(A)and/or on Cp^(B) and/or the positions of each substituent on Cp^(A)and/or on Cp^(B) are independent of each other. For instance, two ormore substituents on Cp^(A) can be different, or alternatively, eachsubstituent on Cp^(A) can be the same. Additionally or alternatively,two or more substituents on Cp^(B) can be different, or alternatively,all substituents on Cp^(B) can be the same. In another aspect, one ormore of the substituents on Cp^(A) can be different from the one or moreof the substituents on Cp^(B), or alternatively, all substituents onboth Cp^(A) and/or on Cp^(B) can be the same. In these and otheraspects, each substituent can be at any position on the respectivecyclopentadienyl or indenyl ring structure. If substituted, Cp^(A)and/or Cp^(B) independently can have one substituent, two substituents,three substituents, four substituents, and so forth.

In formula (I), each substituent on Cp^(A) and/or on Cp^(B)independently can be H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or aC₁ to C₃₆ hydrocarbylsilyl group. In some aspects, each substituentindependently can be H; alternatively, a halide; alternatively, a C₁ toC₁₈ hydrocarbyl group; alternatively, a C₁ to C₁₈ halogenatedhydrocarbyl group; alternatively, a C₁ to C₁₈ hydrocarboxy group;alternatively, a C₁ to C₁₈ hydrocarbylsilyl group; alternatively, a C₁to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group; oralternatively, a C₁ to C₈ alkyl group or a C₃ to C₈ alkenyl group. Thehalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, andC₁ to C₃₆ hydrocarbylsilyl group which can be a substituent on Cp^(A)and/or on Cp^(B) in formula (I) can be any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, and C₁ to C₃₆ hydrocarbylsilylgroup described herein (e.g., as pertaining to X in formula (I)). Asubstituent on Cp^(A) and/or on Cp^(B) in formula (I) can be, in certainaspects, a C₁ to C₃₆ halogenated hydrocarbyl group, where thehalogenated hydrocarbyl group indicates the presence of one or morehalogen atoms replacing an equivalent number of hydrogen atoms in thehydrocarbyl group. The halogenated hydrocarbyl group often can be ahalogenated alkyl group, a halogenated alkenyl group, a halogenatedcycloalkyl group, a halogenated aryl group, or a halogenated aralkylgroup. Representative and non-limiting halogenated hydrocarbyl groupsinclude pentafluorophenyl, trifluoromethyl (CF₃), and the like.

As a non-limiting example, if present, each substituent on Cp^(A) and/orCp^(B) independently can be H, Cl, CF₃, a methyl group, an ethyl group,a propyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, anethenyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a heptenyl group, an octenyl group, a nonenyl group, adecenyl group, a phenyl group, a tolyl group (or other substituted arylgroup), a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group; alternatively, H; alternatively, Cl;alternatively, CF₃; alternatively, a methyl group; alternatively, anethyl group; alternatively, a propyl group; alternatively, a butylgroup; alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group, a nonylgroup; alternatively, a decyl group; alternatively, an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; alternatively, a hexenyl group;alternatively, a heptenyl group; alternatively, an octenyl group;alternatively, a nonenyl group; alternatively, a decenyl group;alternatively, a phenyl group; alternatively, a tolyl group;alternatively, a benzyl group; alternatively, a naphthyl group;alternatively, a trimethylsilyl group; alternatively, atriisopropylsilyl group; alternatively, a triphenylsilyl group; oralternatively, an allyldimethylsilyl group.

Illustrative and non-limiting examples of unbridged metallocenecompounds having formula (I) and/or suitable for use as catalystcomponent I can include the following compounds (Ph=phenyl):

and the like, as well as combinations thereof.

Catalyst component I is not limited solely to unbridged metallocenecompounds such as described above, or to suitable unbridged metallocenecompounds disclosed in U.S. Pat. Nos. 7,199,073, 7,226,886, 7,312,283,and 7,619,047, which are incorporated herein by reference in theirentirety. For example, catalyst component I can comprise an unbridgedzirconium and/or hafnium based dinuclear metallocene compound. In oneaspect, catalyst component I can comprise an unbridged zirconium basedhomodinuclear metallocene compound. In another aspect, catalystcomponent I can comprise an unbridged hafnium based homodinuclearmetallocene compound. In yet another aspect, catalyst component I cancomprise an unbridged zirconium and/or hafnium based heterodinuclearmetallocene compound (i.e., dinuclear compound with two hafniums, or twozirconiums, or one zirconium and one hafnium). Catalyst component I cancomprise unbridged dinuclear metallocenes such as those described inU.S. Pat. Nos. 7,919,639 and 8,080,681, the disclosures of which areincorporated herein by reference in their entirety. Illustrative andnon-limiting examples of dinuclear metallocene compounds suitable foruse as catalyst component I can include the following compounds:

and the like, as well as combinations thereof.Catalyst Component II

Catalyst component II can comprise a bridged metallocene compound. Inone aspect, for instance, catalyst component II can comprise a bridgedzirconium or hafnium based metallocene compound. In another aspect,catalyst component II can comprise a bridged zirconium or hafnium basedmetallocene compound with an alkenyl substituent. In yet another aspect,catalyst component II can comprise a bridged zirconium or hafnium basedmetallocene compound with an alkenyl substituent and a fluorenyl group.In still another aspect, catalyst component II can comprise a bridgedzirconium or hafnium based metallocene compound with a cyclopentadienylgroup and a fluorenyl group, and with an alkenyl substituent on thebridging group and/or on the cyclopentadienyl group.

In some aspects, catalyst component II can comprise a bridgedmetallocene compound having an aryl group substituent on the bridginggroup, while in other aspects, catalyst component II can comprise adinuclear bridged metallocene compound with an alkenyl linking group.

Catalyst component II can comprise, in particular aspects of thisinvention, a bridged metallocene compound having formula (II):

Within formula (II), M, Cp, R^(X), R^(Y), E, and each X are independentelements of the bridged metallocene compound. Accordingly, the bridgedmetallocene compound having formula (II) can be described using anycombination of M, Cp, R^(X), R^(Y), E, and X disclosed herein.

The selections for M and each X in formula (II) are the same as thosedescribed herein above for formula (I). In formula (II), Cp can be asubstituted cyclopentadienyl, indenyl, or fluorenyl group. In oneaspect, Cp can be a substituted cyclopentadienyl group, while in anotheraspect, Cp can be a substituted indenyl group.

In some aspects, Cp can contain no additional substituents, e.g., otherthan bridging group E, discussed further herein below. In other aspects,Cp can be further substituted with one substituent, two substituents,three substituents, four substituents, and so forth. If present, eachsubstituent on Cp independently can be H, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group.Importantly, each substituent on Cp can be either the same or adifferent substituent group. Moreover, each substituent can be at anyposition on the respective cyclopentadienyl, indenyl, or fluorenyl ringstructure that conforms with the rules of chemical valence. In general,any substituent on Cp, independently, can be H or any halide, C₁ to C₃₆hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group described herein(e.g., as pertaining to substituents on Cp^(A) and Cp^(B) in formula(I)).

In one aspect, for example, each substituent on Cp independently can bea C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group. Inanother aspect, each substituent on Cp independently can be a C₁ to C₈alkyl group or a C₃ to C₈ alkenyl group. In yet another aspect, eachsubstituent on Cp^(C) independently can be H, Cl, CF₃, a methyl group,an ethyl group, a propyl group, a butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, anethenyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a heptenyl group, an octenyl group, a nonenyl group, adecenyl group, a phenyl group, a tolyl group, a benzyl group, a naphthylgroup, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, or an allyldimethylsilyl group.

Similarly, R^(X) and R^(Y) in formula (II) independently can be H or anyhalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl groupdisclosed herein (e.g., as pertaining to substituents on Cp^(A) andCp^(B) in formula (I)). In one aspect, for example, R^(X) and R^(Y)independently can be H or a C₁ to C₁₂ hydrocarbyl group. In anotheraspect, R^(X) and R^(Y) independently can be a C₁ to C₁₀ hydrocarbylgroup. In yet another aspect, R^(X) and R^(Y) independently can be H,Cl, CF₃, a methyl group, an ethyl group, a propyl group, a butyl group(e.g., t-Bu), a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolylgroup, a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group, and the like. In still another aspect, R^(X)and R^(Y) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, a decenyl group, a phenylgroup, a tolyl group, or a benzyl group.

Bridging group E in formula (II) can be (i) a bridging group having theformula >E^(A)R^(A)R^(B), wherein E^(A) can be C, Si, or Ge, and R^(A)and R^(B) independently can be H or a C₁ to C₁₈ hydrocarbyl group; (ii)a bridging group having the formula —CR^(C)R^(D)—CR^(E)R^(F)—, whereinR^(C), R^(D), R^(E), and R^(F) independently can H or a C₁ to C₁₈hydrocarbyl group; or (iii) a bridging group having the formula—SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ can be C or Si, and R^(G),R^(H), R^(I), and R^(J) independently can be H or a C₁ to C₁₈hydrocarbyl group.

In the first option, the bridging group E can have the formula>E^(A)R^(A)R^(B), wherein E^(A) can be C, Si, or Ge, and R^(A) and R^(B)independently can be H or any C₁ to C₁₈ hydrocarbyl group disclosedherein. In some aspects of this invention, R^(A) and R^(B) independentlycan be a C₁ to C₁₂ hydrocarbyl group; alternatively, R^(A) and R^(B)independently can be a C₁ to C₈ hydrocarbyl group; alternatively, R^(A)and R^(B) independently can be a phenyl group, a C₁ to C₈ alkyl group,or a C₃ to C₈ alkenyl group; alternatively, R^(A) and R^(B)independently can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, acyclohexylphenyl group, a naphthyl group, a tolyl group, or a benzylgroup; or alternatively, R^(A) and R^(B) independently can be a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ahexyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a phenyl group, or a benzyl group. In these and otheraspects, R^(A) and R^(B) can be either the same or different.

In the second option, the bridging group E can have the formula—CR^(C)R^(D)—CR^(E)R^(F)—, wherein R^(C), R^(D), R^(E), and R^(F)independently can be H or any C₁ to C₁₈ hydrocarbyl group disclosedherein. For instance, R^(C), R^(D), R^(E), and R^(F) independently canbe H or a methyl group.

In the third option, the bridging group E can have the formula—SiR^(G)R^(H)-E⁵R^(I)R^(J)—, wherein E⁵ can be C or Si, and R^(G),R^(H), R^(I), and R^(J) independently can be H or any C₁ to C₁₈hydrocarbyl group disclosed herein. For instance, E⁵ can be Si, andR^(G), R^(H), R^(I), and R^(J) independently can be H or a methyl group.

Illustrative and non-limiting examples of bridged metallocene compoundshaving formula (II) and/or suitable for use as catalyst component II caninclude the following compounds (Me=methyl, Ph=phenyl; t-Bu=tert-butyl):

and the like, as well as combinations thereof.

Further examples of bridged metallocene compounds having formula (II)and/or suitable for use as catalyst component II can include, but arenot limited to, the following compounds:

and the like, as well as combinations thereof.

Catalyst component II is not limited solely to the bridged metallocenecompounds such as described above. Other suitable bridged metallocenecompounds are disclosed in U.S. Pat. Nos. 7,026,494, 7,041,617,7,226,886, 7,312,283, 7,517,939, and 7,619,047, which are incorporatedherein by reference in their entirety.

Catalyst Component III

In some aspects, the catalyst composition can contain catalyst componentIII, which can comprise a half-metallocene compound. Catalyst componentIII can comprise, in particular aspects of this invention, ahalf-metallocene compound having formula (IIIA):

Within formula (IIIA), Ind and each X are independent elements of thehalf-metallocene compound. Accordingly, the half-metallocene compoundhaving formula (IIIA) can be described using any combination of Ind andX disclosed herein. The selections for each X in formula (IIIA) are thesame as those described hereinabove for formula (I), i.e.,independently, any monoanionic ligand disclosed herein.

In formula (IIIA), Ind can be a substituted or unsubstituted indenylgroup. In one aspect, Ind can be an unsubstituted indenyl group.Alternatively, Ind can be a substituted indenyl group, having onesubstituent, two substituents, three substituents, four substituents,five substituents, six substituents, or seven substituents. If present,each substituent on Ind independently can be H, a halide, a C₁ to C₃₆hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ toC₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group.Importantly, each substituent on Ind can be either the same or adifferent substituent group. Moreover, each substituent can be at anyposition on the indenyl ring structure that conforms with the rules ofchemical valence. In general, any substituent on Ind, independently, canbe H or any halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenatedhydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆hydrocarbylsilyl group described herein (e.g., as pertaining tosubstituents on Cp^(A) and Cp^(B) in formula (I)).

In one aspect, for example, each substituent on Ind independently can bea C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂ hydrocarbylsilyl group. Inanother aspect, each substituent on Ind independently can be H, Cl, CF₃,a methyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, an ethenyl group, a propenyl group, a butenyl group, apentenyl group, a hexenyl group, a heptenyl group, an octenyl group, anonenyl group, a decenyl group, a phenyl group, a tolyl group, a benzylgroup, a naphthyl group, a trimethylsilyl group, a triisopropylsilylgroup, a triphenylsilyl group, or an allyldimethylsilyl group.

Illustrative and non-limiting examples of half-metallocene compoundshaving formula (IIIA) and/or suitable for use as catalyst component IIIcan include, but are not limited to, the following compounds:

and the like, as well as combinations thereof.

Half-metallocene compounds having formula (IIIA) can be synthesizedusing any suitable procedure, such as disclosed in Weiss et al.,Organometallics 2005, 24, 2577-2581, which is incorporated herein byreference in its entirety.

Catalyst component III can comprise, in certain aspects of thisinvention, a half-metallocene compound having formula (IIIB):Cr(Cp^(C))(X)(X)(L)_(n)  (IIIB)

Within formula (IIIB), Cp^(C), n, each X and L are independent elementsof the half-metallocene compound. Accordingly, the half-metallocenecompound having formula (IIIB) can be described using any combination ofCp^(C), n, X, and L disclosed herein. The selections for each X informula (IIIB) are the same as those described hereinabove for formula(I), i.e., independently, any monoanionic ligand disclosed herein.

In formula (IIIB), Cp^(C) can be a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group. In one aspect, Cp^(C) canbe an unsubstituted cyclopentadienyl, indenyl, or fluorenyl group;alternatively, an unsubstituted cyclopentadienyl group; alternatively,an unsubstituted indenyl group; or alternatively, an unsubstitutedfluorenyl group. In another aspect, Cp^(C) can be a substitutedcyclopentadienyl, indenyl, or fluorenyl group; alternatively, asubstituted cyclopentadienyl group; alternatively, a substituted indenylgroup; or alternatively, a substituted fluorenyl group. Cp^(C) can be asubstituted cyclopentadienyl, indenyl, or fluorenyl group, having onesubstituent, two substituents, three substituents, four substituents,five substituents, and so forth; each substituent on Cp^(C) can beeither the same or a different substituent group; and each substituentcan be at any position on the ring structure that conforms with therules of chemical valence.

When present, each substituent independently can be H, a halide, a C₁ toC₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁to C₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group. Ingeneral, any substituent on Cp^(C), independently, can be H or anyhalide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbylgroup, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl groupdescribed herein (e.g., as pertaining to substituents on Cp^(A) andCp^(B) in formula (I)).

Each L in formula (IIIB) independently can be a neutral ligand, and theinteger n in formula (IIIB) can be 0, 1 or 2 (e.g., n can be 0 or 1).Suitable neutral ligands are described in U.S. Pat. No. 8,501,882, thedisclosure of which is incorporated herein by reference in its entirety.Typically, each neutral ligand, L, independently can be an ether, athioether, an amine, a nitrile, or a phosphine. For example, eachneutral ligand independently can be azetidine, oxetane, thietane,dioxetane, dithietane, tetrahydropyrrole, dihydropyrrole, pyrrole,indole, isoindole, tetrahydrofuran, 2-methyltetrahydrofuran,2,5-dimethyltetrahydrofuran, dihydrofuran, furan, benzofuran,isobenzofuran, tetrahydrothiophene, dihydrothiophene, thiophene,benzothiophene, isobenzothiophene, imidazolidine, pyrazole, imidazole,oxazolidine, oxazole, isoxazole, thiazolidine, thiazole, isothiazole,benzothiazole, dioxolane, dithiolane, triazole, dithiazole, piperidine,pyridine, dimethyl amine, diethyl amine, tetrahydropyran, dihydropyran,pyran, thiane, piperazine, diazine, oxazine, thiazine, dithiane,dioxane, dioxin, triazine, triazinane, trioxane, oxepin, azepine,thiepin, diazepine, morpholine, quinoline, tetrahydroquinone,bicyclo[3.3.1]tetrasiloxane, or acetonitrile; alternatively, azetidine,oxetane, thietane, dioxetane, dithietane, tetrahydropyrrole,tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,tetrahydrothiophene, imidazolidine, oxazolidine, oxazole, thiazolidine,thiazole, dioxolane, dithiolane, piperidine, tetrahydropyran, pyran,thiane, piperazine, oxazine, thiazine, dithiane, dioxane, dioxin,triazinane, trioxane, azepine, thiepin, diazepine, morpholine,1,2-thiazole, or bicyclo[3.3.1]tetrasiloxane; alternatively,tetrahydropyrrole, tetrahydrofuran, 2-methyltetrahydrofuran,2,5-dimethyltetrahydrofuran, tetrahydrothiophene, oxazolidine,thiazolidine, dioxolane, dithiolane, dithiazole, piperidine,tetrahydropyran, pyran, thiane, piperazine, dithiane, dioxane, dioxin,trioxane, or morpholine, and the like.

Activator-Supports

The present invention encompasses various catalyst compositionscontaining an activator, such as activator-support. In one aspect, theactivator-support can comprise a chemically-treated solid oxide, e.g., asolid oxide treated with an electron-withdrawing anion. Alternatively,in another aspect, the activator-support can comprise a clay mineral, apillared clay, an exfoliated clay, an exfoliated clay gelled intoanother oxide matrix, a layered silicate mineral, a non-layered silicatemineral, a layered aluminosilicate mineral, a non-layeredaluminosilicate mineral, or combinations thereof.

Generally, chemically-treated solid oxides exhibit enhanced acidity ascompared to the corresponding untreated solid oxide. Thechemically-treated solid oxide also can function as a catalyst activatoras compared to the corresponding untreated solid oxide. While thechemically-treated solid oxide can activate a metallocene complex in theabsence of co-catalysts, it is not necessary to eliminate co-catalystsfrom the catalyst composition. The activation function of theactivator-support can enhance the activity of catalyst composition as awhole, as compared to a catalyst composition containing thecorresponding untreated solid oxide. However, it is believed that thechemically-treated solid oxide can function as an activator, even in theabsence of organoaluminum compounds, aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and the like.

The chemically-treated solid oxide can comprise a solid oxide treatedwith an electron-withdrawing anion. While not intending to be bound bythe following statement, it is believed that treatment of the solidoxide with an electron-withdrawing component augments or enhances theacidity of the oxide. Thus, either the activator-support exhibits Lewisor Brønsted acidity that is typically greater than the Lewis or Brønstedacid strength of the untreated solid oxide, or the activator-support hasa greater number of acid sites than the untreated solid oxide, or both.One method to quantify the acidity of the chemically-treated anduntreated solid oxide materials can be by comparing the polymerizationactivities of the treated and untreated oxides under acid catalyzedreactions.

Chemically-treated solid oxides of this invention generally can beformed from an inorganic solid oxide that exhibits Lewis acidic orBrønsted acidic behavior and has a relatively high porosity. The solidoxide can be chemically-treated with an electron-withdrawing component,typically an electron-withdrawing anion, to form an activator-support.

According to one aspect of the present invention, the solid oxide usedto prepare the chemically-treated solid oxide can have a pore volumegreater than about 0.1 cc/g. According to another aspect of the presentinvention, the solid oxide can have a pore volume greater than about 0.5cc/g. According to yet another aspect of the present invention, thesolid oxide can have a pore volume greater than about 1.0 cc/g.

In another aspect, the solid oxide can have a surface area of from about100 to about 1000 m²/g. In yet another aspect, the solid oxide can havea surface area of from about 200 to about 800 m²/g. In still anotheraspect of the present invention, the solid oxide can have a surface areaof from about 250 to about 600 m²/g.

The chemically-treated solid oxide can comprise a solid inorganic oxidecomprising oxygen and one or more elements selected from Group 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, orcomprising oxygen and one or more elements selected from the lanthanideor actinide elements (See: Hawley's Condensed Chemical Dictionary,11^(th) Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G.,Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6^(th)Ed Wiley-Interscience, 1999). For example, the inorganic oxide cancomprise oxygen and an element, or elements, selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn, and Zr.

Suitable examples of solid oxide materials or compounds that can be usedto form the chemically-treated solid oxide can include, but are notlimited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃,Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂,TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxidesthereof, and combinations thereof. For example, the solid oxide cancomprise silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or anycombination thereof.

The solid oxide of this invention encompasses oxide materials such asalumina, “mixed oxides” thereof such as silica-alumina, materials whereone oxide is coated with another, as well as any combinations andmixtures thereof. The mixed oxide compounds such as silica-alumina canbe single or multiple chemical phases with more than one metal combinedwith oxygen to form a solid oxide compound. Examples of mixed oxidesthat can be used in the activator-support of the present invention,either singly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, zeolites, various clayminerals, alumina-titania, alumina-zirconia, zinc-aluminate,alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia,and the like. The solid oxide of this invention also encompasses oxidematerials such as silica-coated alumina, as described in U.S. Pat. No.7,884,163, the disclosure of which is incorporated herein by referencein its entirety.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspectof the present invention, the electron-withdrawing component can be anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anions caninclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, and the like, including mixtures andcombinations thereof. In addition, other ionic or non-ionic compoundsthat serve as sources for these electron-withdrawing anions also can beemployed in the present invention. It is contemplated that theelectron-withdrawing anion can be, or can comprise, fluoride, chloride,bromide, phosphate, triflate, bisulfate, or sulfate, and the like, orany combination thereof, in some aspects of this invention. In otheraspects, the electron-withdrawing anion can comprise sulfate, bisulfate,fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate,phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof.

Thus, for example, the activator-support (e.g., chemically-treated solidoxide) used in the catalyst compositions of the present invention canbe, or can comprise, fluorided alumina, chlorided alumina, bromidedalumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof.In one aspect, the activator-support can be, or can comprise, fluoridedalumina, sulfated alumina, fluorided silica-alumina, sulfatedsilica-alumina, fluorided silica-coated alumina, sulfated silica-coatedalumina, phosphated silica-coated alumina, and the like, or anycombination thereof. In another aspect, the activator-support cancomprise fluorided alumina; alternatively, chlorided alumina;alternatively, sulfated alumina; alternatively, fluoridedsilica-alumina; alternatively, sulfated silica-alumina; alternatively,fluorided silica-zirconia; alternatively, chlorided silica-zirconia; oralternatively, fluorided silica-coated alumina. In yet another aspect,the activator-support can comprise a fluorided solid oxide and/or asulfated solid oxide.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beselected from any cation that allows the salt to revert or decomposeback to the acid before and/or during calcining. Factors that dictatethe suitability of the particular salt to serve as a source for theelectron-withdrawing anion can include, but are not limited to, thesolubility of the salt in the desired solvent, the lack of adversereactivity of the cation, ion-pairing effects between the cation andanion, hygroscopic properties imparted to the salt by the cation, andthe like, and thermal stability of the anion. Examples of suitablecations in the salt of the electron-withdrawing anion can include, butare not limited to, ammonium, trialkyl ammonium, tetraalkyl ammonium,tetraalkyl phosphonium, H⁺, [H(OEt₂)₂]⁺, and the like.

Further, combinations of two or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components can be contacted with the oxide materialsimultaneously or individually, and in any order that affords thedesired chemically-treated solid oxide acidity. For example, one aspectof this invention can employ two or more electron-withdrawing anionsource compounds in two or more separate contacting steps.

Thus, a process by which a chemically-treated solid oxide can beprepared is as follows: a selected solid oxide, or combination of solidoxides, can be contacted with a first electron-withdrawing anion sourcecompound to form a first mixture; this first mixture can be calcined andthen contacted with a second electron-withdrawing anion source compoundto form a second mixture; the second mixture then can be calcined toform a treated solid oxide. In such a process, the first and secondelectron-withdrawing anion source compounds can be either the same ordifferent compounds.

According to another aspect of the present invention, thechemically-treated solid oxide can comprise a solid inorganic oxidematerial, a mixed oxide material, or a combination of inorganic oxidematerials, that is chemically-treated with an electron-withdrawingcomponent, and optionally treated with a metal source, including metalsalts, metal ions, or other metal-containing compounds. Non-limitingexamples of the metal or metal ion can include zinc, nickel, vanadium,titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium,and the like, or combinations thereof. Examples of chemically-treatedsolid oxides that contain a metal or metal ion can include, but are notlimited to, chlorided zinc-impregnated alumina, fluoridedtitanium-impregnated alumina, fluorided zinc-impregnated alumina,chlorided zinc-impregnated silica-alumina, fluorided zinc-impregnatedsilica-alumina, sulfated zinc-impregnated alumina, chlorided zincaluminate, fluorided zinc aluminate, sulfated zinc aluminate,silica-coated alumina treated with hexafluorotitanic acid, silica-coatedalumina treated with zinc and then fluorided, and the like, or anycombination thereof.

Any method of impregnating the solid oxide material with a metal can beused. The method by which the oxide is contacted with a metal source,typically a salt or metal-containing compound, can include, but is notlimited to, gelling, co-gelling, impregnation of one compound ontoanother, and the like. If desired, the metal-containing compound can beadded to or impregnated into the solid oxide in solution form, andsubsequently converted into the supported metal upon calcining.Accordingly, the solid inorganic oxide can further comprise a metalselected from zinc, titanium, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, and the like, or combinations of thesemetals. For example, zinc often can be used to impregnate the solidoxide because it can provide improved catalyst activity at a low cost.

The solid oxide can be treated with metal salts or metal-containingcompounds before, after, or at the same time that the solid oxide istreated with the electron-withdrawing anion. Following any contactingmethod, the contacted mixture of solid compound, electron-withdrawinganion, and the metal ion can be calcined. Alternatively, a solid oxidematerial, an electron-withdrawing anion source, and the metal salt ormetal-containing compound can be contacted and calcined simultaneously.

Various processes can be used to form the chemically-treated solid oxideuseful in the present invention. The chemically-treated solid oxide cancomprise the contact product of one or more solid oxides with one ormore electron-withdrawing anion sources. It is not required that thesolid oxide be calcined prior to contacting the electron-withdrawinganion source. Typically, the contact product can be calcined eitherduring or after the solid oxide is contacted with theelectron-withdrawing anion source. The solid oxide can be calcined oruncalcined. Various processes to prepare solid oxide activator-supportsthat can be employed in this invention have been reported. For example,such methods are described in U.S. Pat. Nos. 6,107,230, 6,165,929,6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017,6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583,6,613,712, 6,632,894, 6,667,274, and 6,750,302, the disclosures of whichare incorporated herein by reference in their entirety.

According to one aspect of the present invention, the solid oxidematerial can be chemically-treated by contacting it with anelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material optionally can be treated witha metal ion, and then calcined to form a metal-containing ormetal-impregnated chemically-treated solid oxide. According to anotheraspect of the present invention, the solid oxide material andelectron-withdrawing anion source can be contacted and calcinedsimultaneously.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include, but is not limited to, gelling, co-gelling, impregnation ofone compound onto another, and the like. Thus, following any contactingmethod, the contacted mixture of the solid oxide, electron-withdrawinganion, and optional metal ion, can be calcined.

The solid oxide activator-support (i.e., chemically-treated solid oxide)thus can be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with anelectron-withdrawing anion source compound (or compounds) to form afirst mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

According to another aspect of the present invention, the solid oxideactivator-support (chemically-treated solid oxide) can be produced by aprocess comprising:

1) contacting a solid oxide (or solid oxides) with a firstelectron-withdrawing anion source compound to form a first mixture;

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support.

According to yet another aspect of the present invention, thechemically-treated solid oxide can be produced or formed by contactingthe solid oxide with the electron-withdrawing anion source compound,where the solid oxide compound is calcined before, during, or aftercontacting the electron-withdrawing anion source, and where there is asubstantial absence of aluminoxanes, organoboron or organoboratecompounds, and ionizing ionic compounds.

Calcining of the treated solid oxide generally can be conducted in anambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. Calcining can be conducted at a temperatureof from about 300° C. to about 800° C., or alternatively, at atemperature of from about 400° C. to about 700° C. Calcining can beconducted for about 30 minutes to about 50 hours, or for about 1 hour toabout 15 hours. Thus, for example, calcining can be carried out forabout 1 to about 10 hours at a temperature of from about 350° C. toabout 550° C. Any suitable ambient atmosphere can be employed duringcalcining. Generally, calcining can be conducted in an oxidizingatmosphere, such as air. Alternatively, an inert atmosphere, such asnitrogen or argon, or a reducing atmosphere, such as hydrogen or carbonmonoxide, can be used.

According to one aspect of the present invention, the solid oxidematerial can be treated with a source of halide ion, sulfate ion, or acombination of anions, optionally treated with a metal ion, and thencalcined to provide the chemically-treated solid oxide in the form of aparticulate solid. For example, the solid oxide material can be treatedwith a source of sulfate (termed a “sulfating agent”), a source ofbromide ion (termed a “bromiding agent”), a source of chloride ion(termed a “chloriding agent”), a source of fluoride ion (termed a“fluoriding agent”), or a combination thereof, and calcined to providethe solid oxide activator. Useful acidic activator-supports can include,but are not limited to, bromided alumina, chlorided alumina, fluoridedalumina, sulfated alumina, bromided silica-alumina, chloridedsilica-alumina, fluorided silica-alumina, sulfated silica-alumina,bromided silica-zirconia, chlorided silica-zirconia, fluoridedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,alumina treated with hexafluorotitanic acid, silica-coated aluminatreated with hexafluorotitanic acid, silica-alumina treated withhexafluorozirconic acid, silica-alumina treated with trifluoroaceticacid, fluorided boria-alumina, silica treated with tetrafluoroboricacid, alumina treated with tetrafluoroboric acid, alumina treated withhexafluorophosphoric acid, a pillared clay, such as a pillaredmontmorillonite, optionally treated with fluoride, chloride, or sulfate;phosphated alumina or other aluminophosphates optionally treated withsulfate, fluoride, or chloride; or any combination of the above.Further, any of these activator-supports optionally can be treated orimpregnated with a metal ion.

In an aspect, the chemically-treated solid oxide can comprise afluorided solid oxide in the form of a particulate solid. The fluoridedsolid oxide can be formed by contacting a solid oxide with a fluoridingagent. The fluoride ion can be added to the oxide by forming a slurry ofthe oxide in a suitable solvent such as alcohol or water including, butnot limited to, the one to three carbon alcohols because of theirvolatility and low surface tension. Examples of suitable fluoridingagents can include, but are not limited to, hydrofluoric acid (HF),ammonium fluoride (NH₄F), ammonium bifluoride (NH₄HF₂), ammoniumtetrafluoroborate (NH₄BF₄), ammonium silicofluoride (hexafluorosilicate)((NH₄)₂SiF₆), ammonium hexafluorophosphate (NH₄PF₆), hexafluorotitanicacid (H₂TiF₆), ammonium hexafluorotitanic acid ((NH₄)₂TiF₆),hexafluorozirconic acid (H₂ZrF₆), AlF₃, NH₄AlF₄, analogs thereof, andcombinations thereof. Triflic acid and ammonium triflate also can beemployed. For example, ammonium bifluoride (NH₄HF₂) can be used as thefluoriding agent, due to its ease of use and availability.

If desired, the solid oxide can be treated with a fluoriding agentduring the calcining step. Any fluoriding agent capable of thoroughlycontacting the solid oxide during the calcining step can be used. Forexample, in addition to those fluoriding agents described previously,volatile organic fluoriding agents can be used. Examples of volatileorganic fluoriding agents useful in this aspect of the invention caninclude, but are not limited to, freons, perfluorohexane,perfluorobenzene, fluoromethane, trifluoroethanol, and the like, andcombinations thereof. Calcining temperatures generally must be highenough to decompose the compound and release fluoride. Gaseous hydrogenfluoride (HF) or fluorine (F₂) itself also can be used with the solidoxide if fluorided while calcining. Silicon tetrafluoride (SiF₄) andcompounds containing tetrafluoroborate (BF₄ ⁻) also can be employed. Oneconvenient method of contacting the solid oxide with the fluoridingagent can be to vaporize a fluoriding agent into a gas stream used tofluidize the solid oxide during calcination. Other suitable fluoridingagents and procedures for preparing fluorided solid oxides are wellknown to those of skill in the art.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide can comprise a chlorided solid oxide in the form of aparticulate solid. The chlorided solid oxide can be formed by contactinga solid oxide with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Thesolid oxide can be treated with a chloriding agent during the calciningstep. Any chloriding agent capable of serving as a source of chlorideand thoroughly contacting the oxide during the calcining step can beused, such as SiCl₄, SiMe₂Cl₂, TiCl₄, BCl₃, and the like, includingmixtures thereof. Volatile organic chloriding agents can be used.Examples of suitable volatile organic chloriding agents can include, butare not limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, andthe like, or any combination thereof. Gaseous hydrogen chloride orchlorine itself also can be used with the solid oxide during calcining.One convenient method of contacting the oxide with the chloriding agentcan be to vaporize a chloriding agent into a gas stream used to fluidizethe solid oxide during calcination. Other suitable chloriding agents andprocedures for preparing chlorided solid oxides are well known to thoseof skill in the art.

The amount of fluoride or chloride ion present before calcining thesolid oxide generally can be from about 1 to about 50% by weight, wherethe weight percent is based on the weight of the solid oxide, forexample, silica-alumina, before calcining. According to another aspectof this invention, the amount of fluoride or chloride ion present beforecalcining the solid oxide can be from about 1 to about 25% by weight,and according to another aspect of this invention, from about 2 to about20% by weight. According to yet another aspect of this invention, theamount of fluoride or chloride ion present before calcining the solidoxide can be from about 4 to about 10% by weight. Once impregnated witha halide, the halided oxide can be dried by any suitable methodincluding, but not limited to, suction filtration followed byevaporation, drying under vacuum, spray drying, and the like, althoughit is also possible to initiate the calcining step immediately withoutdrying the impregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina typicallycan have a pore volume greater than about 0.5 cc/g. According to oneaspect of the present invention, the pore volume can be greater thanabout 0.8 cc/g, and according to another aspect of the presentinvention, greater than about 1.0 cc/g. Further, the silica-aluminagenerally can have a surface area greater than about 100 m²/g. Accordingto another aspect of this invention, the surface area can be greaterthan about 250 m²/g. Yet, in another aspect, the surface area can begreater than about 350 m²/g.

The silica-alumina utilized in the present invention typically can havean alumina content from about 5 to about 95% by weight. According to oneaspect of this invention, the alumina content of the silica-alumina canbe from about 5 to about 50%, or from about 8% to about 30%, alumina byweight. In another aspect, high alumina content silica-alumina compoundscan be employed, in which the alumina content of these silica-aluminacompounds typically ranges from about 60% to about 90%, or from about65% to about 80%, alumina by weight. According to yet another aspect ofthis invention, the solid oxide component can comprise alumina withoutsilica, and according to another aspect of this invention, the solidoxide component can comprise silica without alumina.

The sulfated solid oxide can comprise sulfate and a solid oxidecomponent, such as alumina or silica-alumina, in the form of aparticulate solid. Optionally, the sulfated oxide can be treated furtherwith a metal ion such that the calcined sulfated oxide comprises ametal. According to one aspect of the present invention, the sulfatedsolid oxide can comprise sulfate and alumina. In some instances, thesulfated alumina can be formed by a process wherein the alumina istreated with a sulfate source, for example, sulfuric acid or a sulfatesalt such as ammonium sulfate. This process generally can be performedby forming a slurry of the alumina in a suitable solvent, such asalcohol or water, in which the desired concentration of the sulfatingagent has been added. Suitable organic solvents can include, but are notlimited to, the one to three carbon alcohols because of their volatilityand low surface tension.

According to one aspect of this invention, the amount of sulfate ionpresent before calcining can be from about 0.5 to about 100 parts byweight sulfate ion to about 100 parts by weight solid oxide. Accordingto another aspect of this invention, the amount of sulfate ion presentbefore calcining can be from about 1 to about 50 parts by weight sulfateion to about 100 parts by weight solid oxide, and according to stillanother aspect of this invention, from about 5 to about 30 parts byweight sulfate ion to about 100 parts by weight solid oxide. Theseweight ratios are based on the weight of the solid oxide beforecalcining. Once impregnated with sulfate, the sulfated oxide can bedried by any suitable method including, but not limited to, suctionfiltration followed by evaporation, drying under vacuum, spray drying,and the like, although it is also possible to initiate the calciningstep immediately.

According to another aspect of the present invention, theactivator-support used in preparing the catalyst compositions of thisinvention can comprise an ion-exchangeable activator-support including,but not limited to, silicate and aluminosilicate compounds or minerals,either with layered or non-layered structures, and combinations thereof.In another aspect of this invention, ion-exchangeable, layeredaluminosilicates such as pillared clays can be used asactivator-supports. When the acidic activator-support comprises anion-exchangeable activator-support, it can optionally be treated with atleast one electron-withdrawing anion such as those disclosed herein,though typically the ion-exchangeable activator-support is not treatedwith an electron-withdrawing anion.

According to another aspect of the present invention, theactivator-support of this invention can comprise clay minerals havingexchangeable cations and layers capable of expanding. Typical claymineral activator-supports can include, but are not limited to,ion-exchangeable, layered aluminosilicates such as pillared clays.Although the term “support” is used, it is not meant to be construed asan inert component of the catalyst composition, but rather can beconsidered an active part of the catalyst composition, because of itsintimate association with the metallocene component.

According to another aspect of the present invention, the clay materialsof this invention can encompass materials either in their natural stateor that have been treated with various ions by wetting, ion exchange, orpillaring. Typically, the clay material activator-support of thisinvention can comprise clays that have been ion exchanged with largecations, including polynuclear, highly charged metal complex cations.However, the clay material activator-supports of this invention also canencompass clays that have been ion exchanged with simple salts,including, but not limited to, salts of Al(III), Fe(II), Fe(III), andZn(II) with ligands such as halide, acetate, sulfate, nitrate, ornitrite.

According to another aspect of the present invention, theactivator-support can comprise a pillared clay. The term “pillared clay”is used to refer to clay materials that have been ion exchanged withlarge, typically polynuclear, highly charged metal complex cations.Examples of such ions can include, but are not limited to, Keggin ionswhich can have charges such as 7+, various polyoxometallates, and otherlarge ions. Thus, the term pillaring can refer to a simple exchangereaction in which the exchangeable cations of a clay material arereplaced with large, highly charged ions, such as Keggin ions. Thesepolymeric cations then can be immobilized within the interlayers of theclay and when calcined are converted to metal oxide “pillars,”effectively supporting the clay layers as column-like structures. Thus,once the clay is dried and calcined to produce the supporting pillarsbetween clay layers, the expanded lattice structure can be maintainedand the porosity can be enhanced. The resulting pores can vary in shapeand size as a function of the pillaring material and the parent claymaterial used. Examples of pillaring and pillared clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J. M. Thomas,Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3,pp. 55-99, Academic Press, Inc., (1972); U.S. Pat. No. 4,452,910; U.S.Pat. No. 5,376,611; and U.S. Pat. No. 4,060,480; the disclosures ofwhich are incorporated herein by reference in their entirety.

The pillaring process can utilize clay minerals having exchangeablecations and layers capable of expanding. Any pillared clay that canenhance the polymerization of olefins in the catalyst composition of thepresent invention can be used. Therefore, suitable clay minerals forpillaring can include, but are not limited to, allophanes; smectites,both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereofsuch as montmorillonites (bentonites), nontronites, hectorites, orlaponites; halloysites; vermiculites; micas; fluoromicas; chlorites;mixed-layer clays; the fibrous clays including but not limited tosepiolites, attapulgites, and palygorskites; a serpentine clay; illite;laponite; saponite; and any combination thereof. In one aspect, thepillared clay activator-support can comprise bentonite ormontmorillonite. The principal component of bentonite ismontmorillonite.

The pillared clay can be pretreated if desired. For example, a pillaredbentonite can be pretreated by drying at about 300° C. under an inertatmosphere, typically dry nitrogen, for about 3 hours, before beingadded to the polymerization reactor. Although an exemplary pretreatmentis described herein, it should be understood that the preheating can becarried out at many other temperatures and times, including anycombination of temperature and time steps, all of which are encompassedby this invention.

The activator-support used to prepare the catalyst compositions of thepresent invention can be combined with other inorganic supportmaterials, including, but not limited to, zeolites, inorganic oxides,and the like. In one aspect, typical support materials that can be usedinclude, but are not limited to, silica, silica-alumina, alumina,titania, zirconia, magnesia, boria, thoria, aluminophosphate, aluminumphosphate, silica-titania, coprecipitated silica/titania, mixturesthereof, or any combination thereof.

According to another aspect of the present invention, one or more of themetallocene compounds can be precontacted with an olefin monomer and anorganoaluminum compound for a first period of time prior to contactingthis mixture with the activator-support. Once the precontacted mixtureof metallocene complex(es), olefin monomer, and organoaluminum compoundis contacted with the activator-support, the composition furthercomprising the activator-support can be termed a “postcontacted”mixture. The postcontacted mixture can be allowed to remain in furthercontact for a second period of time prior to being charged into thereactor in which the polymerization process will be carried out.

According to yet another aspect of the present invention, one or more ofthe metallocene compounds can be precontacted with an olefin monomer andan activator-support for a first period of time prior to contacting thismixture with the organoaluminum compound. Once the precontacted mixtureof the metallocene complex(es), olefin monomer, and activator-support iscontacted with the organoaluminum compound, the composition furthercomprising the organoaluminum can be termed a “postcontacted” mixture.The postcontacted mixture can be allowed to remain in further contactfor a second period of time prior to being introduced into thepolymerization reactor.

Co-Catalysts

In certain aspects directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some aspects, the metal of the metal hydrocarbyl can be agroup 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some aspects, themetal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metalhydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron,aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium,calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium,or potassium; alternatively, magnesium or calcium; alternatively,lithium; alternatively, sodium; alternatively, potassium; alternatively,magnesium; alternatively, calcium; alternatively, zinc; alternatively,boron; alternatively, aluminum; or alternatively, tin. In some aspects,the metal hydrocarbyl or metal alkyl, with or without a halide, cancomprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl oralkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or analuminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing aco-catalyst (e.g., the activator can comprise a solid oxide treated withan electron-withdrawing anion), the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organozinccompound, an organomagnesium compound, or an organolithium compound, andthis includes any combinations of these materials. In one aspect, theco-catalyst can comprise an organoaluminum compound. In another aspect,the co-catalyst can comprise an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, an organozinccompound, an organomagnesium compound, an organolithium compound, or anycombination thereof. In yet another aspect, the co-catalyst can comprisean aluminoxane compound; alternatively, an organoboron or organoboratecompound; alternatively, an ionizing ionic compound; alternatively, anorganozinc compound; alternatively, an organomagnesium compound; oralternatively, an organolithium compound.

Organoaluminum Compounds

In some aspects, catalyst compositions of the present invention cancomprise one or more organoaluminum compounds. Such compounds caninclude, but are not limited to, compounds having the formula:(R^(Z))₃Al;wherein each R^(Z) independently can be an aliphatic group having from 1to 10 carbon atoms. For example, each R^(Z) independently can be methyl,ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds which can be used in catalystcompositions disclosed herein can include, but are not limited to,compounds having the formula:Al(X⁷)_(m)(X⁸)_(3-m),wherein each X⁷ independently can be a hydrocarbyl; each X⁸independently can be an alkoxide or an aryloxide, a halide, or ahydride; and m can be from 1 to 3, inclusive. Hydrocarbyl is used hereinto specify a hydrocarbon radical group and includes, for instance, aryl,alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkadienyl, alkynyl,aralkyl, aralkenyl, and aralkynyl groups.

In one aspect, each X⁷ independently can be any hydrocarbyl having from1 to about 18 carbon atoms disclosed herein. In another aspect of thepresent invention, each X⁷ independently can be any alkyl having from 1to 10 carbon atoms disclosed herein. For example, each X⁷ independentlycan be methyl, ethyl, propyl, n-butyl, sec-butyl, isobutyl, or hexyl,and the like, in yet another aspect of the present invention.

According to one aspect of the present invention, each X⁸ independentlycan be an alkoxide or an aryloxide, any one of which has from 1 to 18carbon atoms, a halide, or a hydride. In another aspect of the presentinvention, each X⁸ can be selected independently from fluorine andchlorine. Yet, in another aspect, X⁸ can be chlorine.

In the formula, Al(X⁷)_(m)(X⁸)_(3-m), can be a number from 1 to 3,inclusive, and typically, m can be 3. The value of m is not restrictedto be an integer; therefore, this formula can include sesquihalidecompounds or other organoaluminum cluster compounds.

Examples of organoaluminum compounds suitable for use in accordance withthe present invention can include, but are not limited to,trialkylaluminum compounds, dialkylaluminum halide compounds,dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds,and combinations thereof. Specific non-limiting examples of suitableorganoaluminum compounds can include trimethylaluminum (TMA),triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum(TNBA), triisobutylaluminum (TIBA), tri-n-hexyl aluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, di ethyl aluminum chloride, and the like, or combinationsthereof.

The present invention contemplates a method of precontacting ametallocene compound (or compounds) with an organoaluminum compound andan optional olefin monomer to form a precontacted mixture, prior tocontacting this precontacted mixture with an activator-support to form acatalyst composition. When the catalyst composition is prepared in thismanner, typically, though not necessarily, a portion of theorganoaluminum compound can be added to the precontacted mixture andanother portion of the organoaluminum compound can be added to thepostcontacted mixture prepared when the precontacted mixture iscontacted with the solid oxide activator-support. However, the entireorganoaluminum compound can be used to prepare the catalyst compositionin either the precontacting or postcontacting step. Alternatively, allthe catalyst components can be contacted in a single step.

Further, more than one organoaluminum compound can be used in either theprecontacting or the postcontacting step. When an organoaluminumcompound is added in multiple steps, the amounts of organoaluminumcompound disclosed herein include the total amount of organoaluminumcompound used in both the precontacted and postcontacted mixtures, andany additional organoaluminum compound added to the polymerizationreactor. Therefore, total amounts of organoaluminum compounds aredisclosed regardless of whether a single organoaluminum compound or morethan one organoaluminum compound is used.

Aluminoxane Compounds

Certain aspects of the present invention provide a catalyst compositionwhich can comprise an aluminoxane compound. As used herein, the terms“aluminoxane” and “aluminoxane compound” refer to aluminoxane compounds,compositions, mixtures, or discrete species, regardless of how suchaluminoxanes are prepared, formed or otherwise provided. For example, acatalyst composition comprising an aluminoxane compound can be preparedin which aluminoxane is provided as the poly(hydrocarbyl aluminumoxide), or in which aluminoxane is provided as the combination of analuminum alkyl compound and a source of active protons such as water.Aluminoxanes also can be referred to as poly(hydrocarbyl aluminumoxides) or organoaluminoxanes.

The other catalyst components typically can be contacted with thealuminoxane in a saturated hydrocarbon compound solvent, though anysolvent that is substantially inert to the reactants, intermediates, andproducts of the activation step can be used. The catalyst compositionformed in this manner can be collected by any suitable method, forexample, by filtration. Alternatively, the catalyst composition can beintroduced into the polymerization reactor without being isolated.

The aluminoxane compound of this invention can be an oligomeric aluminumcompound comprising linear structures, cyclic structures, or cagestructures, or mixtures of all three. Cyclic aluminoxane compoundshaving the formula:

wherein each R in this formula independently can be a linear or branchedalkyl having from 1 to 10 carbon atoms, and p in this formula can be aninteger from 3 to 20, are encompassed by this invention. The AlRO moietyshown here also can constitute the repeating unit in a linearaluminoxane. Thus, linear aluminoxanes having the formula:

wherein each R in this formula independently can be a linear or branchedalkyl having from 1 to 10 carbon atoms, and q in this formula can be aninteger from 1 to 50, are also encompassed by this invention.

Further, aluminoxanes can have cage structures of the formula R^(t)_(5r+α)R^(b) _(r−α)Al_(4r)O_(3r), wherein each R^(t) independently canbe a terminal linear or branched alkyl group having from 1 to 10 carbonatoms; each R^(b) independently can be a bridging linear or branchedalkyl group having from 1 to 10 carbon atoms; r can be 3 or 4; and a canbe equal to n_(Al(3))−n_(O(2))+n_(O(4)), wherein n_(Al(3)) is the numberof three coordinate aluminum atoms, n_(O(2)) is the number of twocoordinate oxygen atoms, and n_(O(4)) is the number of 4 coordinateoxygen atoms.

Thus, aluminoxanes which can be employed in the catalyst compositions ofthe present invention can be represented generally by formulas such as(R—Al—O)_(p), R(R—Al—O)_(q)AlR₂, and the like. In these formulas, each Rgroup independently can be a linear or branched C₁-C₆ alkyl, such asmethyl, ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxanecompounds that can be used in accordance with the present invention caninclude, but are not limited to, methylaluminoxane, modifiedmethylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Methylaluminoxane, ethylaluminoxane, and iso-butylaluminoxane can beprepared from trimethylaluminum, triethylaluminum, andtriisobutylaluminum, respectively, and sometimes are referred to aspoly(methyl aluminum oxide), poly(ethyl aluminum oxide), andpoly(isobutyl aluminum oxide), respectively. It is also within the scopeof the invention to use an aluminoxane in combination with atrialkylaluminum, such as that disclosed in U.S. Pat. No. 4,794,096,incorporated herein by reference in its entirety.

The present invention contemplates many values of p and q in thealuminoxane formulas (R—Al—O)_(p) and R(R—Al—O)_(q)AlR₂, respectively.In some aspects, p and q can be at least 3. However, depending upon howthe organoaluminoxane is prepared, stored, and used, the value of p andq can vary within a single sample of aluminoxane, and such combinationsof organoaluminoxanes are contemplated herein.

In preparing a catalyst composition containing an aluminoxane, the molarratio of the total moles of aluminum in the aluminoxane (oraluminoxanes) to the total moles of metallocene complexes in thecomposition generally can be between about 1:10 and about 100,000:1. Inanother aspect, the molar ratio can be in a range from about 5:1 toabout 15,000:1. Optionally, aluminoxane can be added to a polymerizationzone in ranges from about 0.01 mg/L to about 1000 mg/L, from about 0.1mg/L to about 100 mg/L, or from about 1 mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures. Examples oforganoaluminoxane preparations are disclosed in U.S. Pat. Nos. 3,242,099and 4,808,561, the disclosures of which are incorporated herein byreference in their entirety. For example, water in an inert organicsolvent can be reacted with an aluminum alkyl compound, such as(R^(Z))₃Al, to form the desired organoaluminoxane compound. While notintending to be bound by this statement, it is believed that thissynthetic method can afford a mixture of both linear and cyclic R—Al—Oaluminoxane species, both of which are encompassed by this invention.Alternatively, organoaluminoxanes can be prepared by reacting analuminum alkyl compound, such as (R^(Z))₃Al, with a hydrated salt, suchas hydrated copper sulfate, in an inert organic solvent.

Organoboron & Organoborate Compounds

According to another aspect of the present invention, the catalystcomposition can comprise an organoboron or organoborate compound. Suchcompounds can include neutral boron compounds, borate salts, and thelike, or combinations thereof. For example, fluoroorgano boron compoundsand fluoroorgano borate compounds are contemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be utilizedwith the present invention. Examples of fluoroorgano borate compoundsthat can be used in the present invention can include, but are notlimited to, fluorinated aryl borates such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, ormixtures thereof. Examples of fluoroorgano boron compounds that can beused as co-catalysts in the present invention can include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)phenyl]boron, and the like, or mixturesthereof. Although not intending to be bound by the following theory,these examples of fluoroorgano borate and fluoroorgano boron compounds,and related compounds, can form “weakly-coordinating” anions whencombined with a transition metal complex (see e.g., U.S. Pat. No.5,919,983, the disclosure of which is incorporated herein by referencein its entirety). Applicants also contemplate the use of diboron, orbis-boron, compounds or other bifunctional compounds containing two ormore boron atoms in the chemical structure, such as disclosed in J. Am.Chem. Soc., 2005, 127, pp. 14756-14768, the content of which isincorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be used. According toone aspect of this invention, the molar ratio of the total moles oforganoboron or organoborate compound (or compounds) to the total molesof metallocene compounds in the catalyst composition can be in a rangefrom about 0.1:1 to about 15:1. Typically, the amount of thefluoroorgano boron or fluoroorgano borate compound used can be fromabout 0.5 moles to about 10 moles of boron/borate compound per mole ofmetallocene complexes. According to another aspect of this invention,the amount of fluoroorgano boron or fluoroorgano borate compound can befrom about 0.8 moles to about 5 moles of boron/borate compound per moleof metallocene complexes.

Ionizing Ionic Compounds

In another aspect, catalyst compositions disclosed herein can comprisean ionizing ionic compound. An ionizing ionic compound is an ioniccompound that can function as a co-catalyst to enhance the activity ofthe catalyst composition. While not intending to be bound by theory, itis believed that the ionizing ionic compound can be capable of reactingwith a metallocene complex and converting the metallocene complex intoone or more cationic metallocene complexes, or incipient cationicmetallocene complexes. Again, while not intending to be bound by theory,it is believed that the ionizing ionic compound can function as anionizing compound by completely or partially extracting an anionicligand, such as monoanionic ligand X, from the metallocene complex.However, the ionizing ionic compound can be a co-catalyst regardless ofwhether it is ionizes the metallocene compound, abstracts a X ligand ina fashion as to form an ion pair, weakens the metal-X bond in themetallocene, simply coordinates to a X ligand, or activates themetallocene by some other mechanism.

Further, it is not necessary that the ionizing ionic compound activatethe metallocene compound only. The activation function of the ionizingionic compound can be evident in the enhanced activity of catalystcomposition as a whole, as compared to a catalyst composition that doesnot contain an ionizing ionic compound.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate, and thelike, or combinations thereof. Ionizing ionic compounds useful in thisinvention are not limited to these; other examples of ionizing ioniccompounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938, thedisclosures of which are incorporated herein by reference in theirentirety.

Organozinc, Organomagnesium, & Organolithium Compounds

Other aspects are directed to catalyst compositions which can include anorganozinc compound, an organomagnesium compound, an organolithiumcompound, or a combination thereof. In some aspects, these compoundshave the following general formulas:Zn(X¹⁰)(X¹¹);Mg(X¹²)(X¹³); andLi(X¹⁴).In these formulas, X¹⁰, X¹², and X¹⁴ independently can be a C₁ to C₁₈hydrocarbyl group, and X¹¹ and X¹³ independently can be H, a halide, ora C₁ to C₁₈ hydrocarbyl or C₁ to C₁₈ hydrocarboxy group. It iscontemplated X¹⁰ and X¹¹ (or X¹² and X¹³) can be the same, or that X¹⁰and X¹¹ (or X¹² and X¹³) can be different.

In one aspect, X¹⁰, X¹¹, X¹², X¹³, and X¹⁴ independently can be any C₁to C₁₈ hydrocarbyl group, C₁ to C₁₂ hydrocarbyl group, C₁ to C₈hydrocarbyl group, or C₁ to C₅ hydrocarbyl group disclosed herein. Inanother aspect, X¹⁰, X¹¹, X¹², X¹³, and X¹⁴ independently can be any C₁to C₁₈ alkyl group, C₂ to C₁₈ alkenyl group, C₆ to C₁₈ aryl group, or C₇to C₁₈ aralkyl group disclosed herein; alternatively, any C₁ to C₁₂alkyl group, C₂ to C₁₂ alkenyl group, C₆ to C₁₂ aryl group, or C₇ to C₁₂aralkyl group disclosed herein; or alternatively, any C₁ to C₅ alkylgroup, C₂ to C₅ alkenyl group, C₆ to C₈ aryl group, or C₇ to C₈ aralkylgroup disclosed herein. Thus, X¹⁰, X¹¹, X¹², X¹³, and X¹⁴ independentlycan be a methyl group, an ethyl group, a propyl group, a butyl group, apentyl group, a hexyl group, a heptyl group, an octyl group, a nonylgroup, a decyl group, a undecyl group, a dodecyl group, a tridecylgroup, a tetradecyl group, a pentadecyl group, a hexadecyl group, aheptadecyl group, an octadecyl group, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, a decenyl group, a undecenylgroup, a dodecenyl group, a tridecenyl group, a tetradecenyl group, apentadecenyl group, a hexadecenyl group, a heptadecenyl group, anoctadecenyl group, a phenyl group, a naphthyl group, a benzyl group, ora tolyl group, and the like. In yet another aspect, X¹⁰, X¹¹, X¹², X¹³,and X¹⁴ independently can be methyl, ethyl, propyl, butyl, or pentyl(e.g., neopentyl), or both X¹⁰ and X¹¹ (or both X¹² and X¹³) can bemethyl, or ethyl, or propyl, or butyl, or pentyl (e.g., neopentyl).

X¹¹ and X¹³ independently can be H, a halide, or a C₁ to C₁₈ hydrocarbylor C₁ to C₁₈ hydrocarboxy group (e.g., any C₁ to C₁₈, C₁ to C₁₂, C₁ toC₁₀, or C₁ to C₈ hydrocarboxy group disclosed herein). In some aspects,X¹¹ and X¹³ independently can be H, a halide (e.g., Cl), or a C₁ to C₁₈hydrocarbyl or C₁ to C₁₈ hydrocarboxy group; alternatively, H, a halide,or a C₁ to C₈ hydrocarbyl or C₁ to C₈ hydrocarboxy group; oralternatively, H, Br, Cl, F, I, methyl, ethyl, propyl, butyl, pentyl(e.g., neopentyl), hexyl, heptyl, octyl, nonyl, decyl, ethenyl,propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,decenyl, phenyl, benzyl, tolyl, methoxy, ethoxy, propoxy, butoxy,pentoxy, phenoxy, toloxy, xyloxy, or benzoxy.

In other aspects, the organozinc and/or the organomagnesium compound canhave one or two hydrocarbylsilyl moieties. Each hydrocarbyl of thehydrocarbylsilyl group can be any hydrocarbyl group disclosed herein(e.g., a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₆ to C₁₈aryl group, a C₇ to C₁₈ aralkyl group, etc.). Illustrative andnon-limiting examples of hydrocarbylsilyl groups can include, but arenot limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (e.g.,triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl,allyldimethylsilyl, trimethylsilylmethyl, and the like.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an aspect, the olefinmonomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect,examples of suitable olefin comonomers can include, but are not limitedto, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, and the like, or combinations thereof. According toanother aspect of the present invention, the olefin monomer can compriseethylene, and the comonomer can comprise a C₃-C₁₀ alpha-olefin;alternatively, the comonomer can comprise 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, styrene, or any combination thereof; alternatively,the comonomer can comprise 1-butene, 1-hexene, 1-octene, or anycombination thereof; alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

Generally, the amount of comonomer introduced into a polymerizationreactor system to produce a copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another aspect of the present invention, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.01 to about 40 weight percent comonomer based on thetotal weight of the monomer and comonomer. In still another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.1 to about 35 weight percent comonomer based on thetotal weight of the monomer and comonomer. Yet, in another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one aspect of the present invention, at least onemonomer/reactant can be ethylene (or propylene), so the polymerizationreaction can be a homopolymerization involving only ethylene (orpropylene), or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the catalyst compositions of this invention can beused in the polymerization of diolefin compounds including, but notlimited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Catalyst Compositions

In some aspects, the present invention can employ catalyst compositionscontaining catalyst component I, catalyst component II, an activator(one or more than one), and optionally, a co-catalyst. In other aspects,the present invention can employ catalyst compositions containingcatalyst component I, catalyst component II, catalyst component III, anactivator (one or more than one), and optionally, a co-catalyst. Thesecatalyst compositions can be utilized to producepolyolefins—homopolymers, copolymers, and the like—for a variety ofend-use applications. Catalyst components I, II, and III are discussedhereinabove. In aspects of the present invention, it is contemplatedthat the catalyst composition can contain more than one catalystcomponent I metallocene compound, and/or more than one catalystcomponent II metallocene compound, and/or more than one catalystcomponent III metallocene compound. Further, additional catalyticcompounds—other than those specified as catalyst component I, II, orIII—can be employed in the catalyst compositions and/or thepolymerization processes, provided that the additional catalyticcompound(s) does not detract from the advantages disclosed herein.Additionally, more than one activator also may be utilized.

The metallocene compounds of catalyst component I are discussedhereinabove. For instance, in some aspects, catalyst component I cancomprise (or consist essentially of, or consist of) an unbridgedmetallocene compound having formula (I). The bridged metallocenecompounds of catalyst component II also are discussed hereinabove. Forinstance, in some aspects, catalyst component II can comprise (orconsist essentially of, or consist of) a metallocene compound havingformula (II). Moreover, the half-metallocene compounds of catalystcomponent III are discussed hereinabove. For instance, in some aspects,catalyst component III can comprise (or consist essentially of, orconsist of) a half-metallocene compound having formula (IIIA) or formula(IIIB).

Generally, catalyst compositions of the present invention can comprisecatalyst component I, catalyst component II, and an activator, oralternatively, catalyst component I, catalyst component II, catalystcomponent III, and an activator. In aspects of the invention, theactivator can comprise an activator-support (e.g., an activator-supportcomprising a solid oxide treated with an electron-withdrawing anion).Activator-supports useful in the present invention are disclosedhereinabove. Optionally, such catalyst compositions can further compriseone or more than one co-catalyst compound or compounds (suitableco-catalysts, such as organoaluminum compounds, also are discussedhereinabove). Thus, a catalyst composition of this invention cancomprise catalyst component I, catalyst component II, anactivator-support (or catalyst component I, catalyst component II,catalyst component III, an activator-support), and an organoaluminumcompound. For instance, the activator-support can comprise (or consistessentially of, or consist of) fluorided alumina, chlorided alumina,bromided alumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof;alternatively, the activator-support can comprise (or consistessentially of, or consist of) a fluorided solid oxide and/or a sulfatedsolid oxide. Additionally, the organoaluminum compound can comprise (orconsist essentially of, or consist of) trimethylaluminum,triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Accordingly, a catalystcomposition consistent with aspects of the invention can comprise (orconsist essentially of, or consist of) an unbridged zirconium or hafniumbased metallocene compound; a bridged zirconium or hafnium basedmetallocene compound with a fluorenyl group; optionally, ahalf-metallocene compound; sulfated alumina (or fluoridedsilica-alumina, or fluorided silica-coated alumina); andtriethylaluminum (or triisobutylaluminum).

In another aspect of the present invention, a catalyst composition isprovided which comprises catalyst component I, catalyst component II (orcatalyst component I, catalyst component II, catalyst component III), anactivator-support, and an organoaluminum compound, wherein this catalystcomposition is substantially free of aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and/or other similarmaterials; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. In these aspects, the catalyst composition has catalystactivity, discussed below, in the absence of these additional materials.For example, a catalyst composition of the present invention can consistessentially of catalyst component I, catalyst component II (or catalystcomponent I, catalyst component II, catalyst component III), anactivator-support, and an organoaluminum compound, wherein no othermaterials are present in the catalyst composition which wouldincrease/decrease the activity of the catalyst composition by more thanabout 10% from the catalyst activity of the catalyst composition in theabsence of said materials.

However, in other aspects of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising catalyst component I, catalyst component II (orcatalyst component I, catalyst component II, catalyst component III),and an activator-support can further comprise an optional co-catalyst.Suitable co-catalysts in this aspect can include, but are not limitedto, aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, or any combination thereof; or alternatively, organoaluminumcompounds, organozinc compounds, organomagnesium compounds,organolithium compounds, or any combination thereof. More than oneco-catalyst can be present in the catalyst composition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition can comprisecatalyst component I, catalyst component II (or catalyst component I,catalyst component II, catalyst component III), and an activator,wherein the activator comprises an aluminoxane compound, an organoboronor organoborate compound, an ionizing ionic compound, or combinationsthereof.

In a particular aspect contemplated herein, the catalyst composition isa catalyst composition comprising an activator (one or more than one),only one catalyst component I metallocene compound, only one catalystcomponent II metallocene compound, and only one catalyst component IIIhalf-metallocene compound (if present). In these and other aspects, thecatalyst composition can comprise an activator (e.g., anactivator-support comprising a solid oxide treated with anelectron-withdrawing anion); only one unbridged zirconium or hafniumbased metallocene compound; only one bridged zirconium or hafnium basedmetallocene compound with a fluorenyl group; and optionally, only onehalf-metallocene compound.

This invention further encompasses methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence.

Catalyst component I, catalyst component II, or catalyst component III,or any combination thereof, can be precontacted with an olefinic monomerif desired, not necessarily the olefin monomer to be polymerized, and anorganoaluminum compound for a first period of time prior to contactingthis precontacted mixture with an activator-support. The first period oftime for contact, the precontact time, between the metallocenecompound(s), the olefinic monomer, and the organoaluminum compoundtypically ranges from a time period of about 1 minute to about 24 hours,for example, from about 3 minutes to about 1 hour. Precontact times fromabout 10 minutes to about 30 minutes also can be employed.Alternatively, the precontacting process can be carried out in multiplesteps, rather than a single step, in which multiple mixtures can beprepared, each comprising a different set of catalyst components. Forexample, at least two catalyst components can be contacted forming afirst mixture, followed by contacting the first mixture with at leastone other catalyst component forming a second mixture, and so forth.

Multiple precontacting steps can be carried out in a single vessel or inmultiple vessels. Further, multiple precontacting steps can be carriedout in series (sequentially), in parallel, or a combination thereof. Forexample, a first mixture of two catalyst components can be formed in afirst vessel, a second mixture comprising the first mixture plus oneadditional catalyst component can be formed in the first vessel or in asecond vessel, which is typically placed downstream of the first vessel.

In another aspect, one or more of the catalyst components can be splitand used in different precontacting treatments. For example, part of acatalyst component can be fed into a first precontacting vessel forprecontacting with at least one other catalyst component, while theremainder of that same catalyst component can be fed into a secondprecontacting vessel for precontacting with at least one other catalystcomponent, or can be fed directly into the reactor, or a combinationthereof. The precontacting can be carried out in any suitable equipment,such as tanks, stirred mix tanks, various static mixing devices, aflask, a vessel of any type, or combinations of these apparatus.

In another aspect of this invention, the various catalyst components(for example, a catalyst component I, II, and/or III metallocene, anactivator-support, an organoaluminum co-catalyst, and optionally anunsaturated hydrocarbon) can be contacted in the polymerization reactorsimultaneously while the polymerization reaction is proceeding.Alternatively, any two or more of these catalyst components can beprecontacted in a vessel prior to entering the reaction zone. Thisprecontacting step can be continuous, in which the precontacted productcan be fed continuously to the reactor, or it can be a stepwise orbatchwise process in which a batch of precontacted product can be addedto make a catalyst composition. This precontacting step can be carriedout over a time period that can range from a few seconds to as much asseveral days, or longer. In this aspect, the continuous precontactingstep generally can last from about 1 second to about 1 hour. In anotheraspect, the continuous precontacting step can last from about 10 secondsto about 45 minutes, or from about 1 minute to about 30 minutes.

In an aspect, once the precontacted mixture of catalyst component Iand/or catalyst component II and/or catalyst component III, an olefinmonomer (if used), and an organoaluminum co-catalyst is contacted withan activator-support, this composition (with the addition of theactivator-support) can be termed the “postcontacted mixture.” Thepostcontacted mixture optionally can remain in contact for a secondperiod of time, the postcontact time, prior to initiating thepolymerization process. Postcontact times between the precontactedmixture and the activator-support generally range from about 1 minute toabout 24 hours. In a further aspect, the postcontact time can be in arange from about 3 minutes to about 1 hour. The precontacting step, thepostcontacting step, or both, can increase the productivity of thepolymer as compared to the same catalyst composition that is preparedwithout precontacting or postcontacting. However, neither aprecontacting step nor a postcontacting step is required.

The postcontacted mixture can be heated at a temperature and for a timeperiod sufficient to allow adsorption, impregnation, or interaction ofthe precontacted mixture and the activator-support, such that a portionof the components of the precontacted mixture can be immobilized,adsorbed, or deposited thereon. Where heating is employed, thepostcontacted mixture generally can be heated to a temperature of frombetween about 0° F. to about 150° F., or from about 40° F. to about 95°F.

According to an aspect of this invention, the weight ratio of catalystcomponent I to catalyst component II in the catalyst composition can bein a range from about 10:1 to about 1:10, from about 8:1 to about 1:8,from about 5:1 to about 1:5, from about 4:1 to about 1:4, from about 3:1to about 1:3; from about 2:1 to about 1:2, from about 1.5:1 to about1:1.5, from about 1.25:1 to about 1:1.25, or from about 1.1:1 to about1:1.1. If present, the weight percentage of catalyst component III inthe catalyst composition can be in a range from about 5 to about 50%,from about 5 to about 45%, from about 5 to about 40%, from about 10 toabout 50%, from about 10 to about 40%, or from about 10 to about 30%.These weight percentages are based on the total weight of catalystcomponents I, II, and III equaling 100%, and does not include othercomponents of the catalyst composition, e.g., activator, co-catalyst,etc.

When a precontacting step is used, the molar ratio of the total moles ofolefin monomer to total moles of metallocene(s) in the precontactedmixture typically can be in a range from about 1:10 to about 100,000:1.Total moles of each component are used in this ratio to account foraspects of this invention where more than one olefin monomer and/or morethan one metallocene compound is employed in a precontacting step.Further, this molar ratio can be in a range from about 10:1 to about1,000:1 in another aspect of the invention.

Generally, the weight ratio of organoaluminum compound toactivator-support can be in a range from about 10:1 to about 1:1000. Ifmore than one organoaluminum compound and/or more than oneactivator-support is employed, this ratio is based on the total weightof each respective component. In another aspect, the weight ratio of theorganoaluminum compound to the activator-support can be in a range fromabout 3:1 to about 1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of metallocenecompounds (total of catalyst component I, II, and optionally III) toactivator-support can be in a range from about 1:1 to about 1:1,000,000.If more than one activator-support is employed, this ratio is based onthe total weight of the activator-support. In another aspect, thisweight ratio can be in a range from about 1:5 to about 1:100,000, orfrom about 1:10 to about 1:10,000. Yet, in another aspect, the weightratio of the metallocene compounds to the activator-support can be in arange from about 1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 100 grams of polyethylene (homopolymer,copolymer, etc., as the context requires) per gram of activator-supportper hour (abbreviated g/g/hr). In another aspect, the catalyst activitycan be greater than about 150, greater than about 250, or greater thanabout 500 g/g/hr. In still another aspect, catalyst compositions of thisinvention can be characterized by having a catalyst activity greaterthan about 550, greater than about 650, or greater than about 750g/g/hr. Yet, in another aspect, the catalyst activity can be greaterthan about 1000 g/g/hr, greater than about 2000 g/g/hr, or greater thanabout 3000 g/g/hr, and often as high as 5000-10,000 g/g/hr. Theseactivities are measured under slurry polymerization conditions, with atriisobutylaluminum co-catalyst, using isobutane as the diluent, at apolymerization temperature of about 90° C. and a reactor pressure ofabout 390 psig. Moreover, in some aspects, the activator-support cancomprise sulfated alumina, fluorided silica-alumina, or fluoridedsilica-coated alumina, although not limited thereto.

As discussed herein, any combination of catalyst component I, catalystcomponent II, catalyst component III (if used), an activator-support, anorganoaluminum compound, and an olefin monomer (if used), can beprecontacted in some aspects of this invention. When any precontactingoccurs with an olefinic monomer, it is not necessary that the olefinmonomer used in the precontacting step be the same as the olefin to bepolymerized. Further, when a precontacting step among any combination ofthe catalyst components is employed for a first period of time, thisprecontacted mixture can be used in a subsequent postcontacting stepbetween any other combination of catalyst components for a second periodof time. For example, one or more metallocene compounds, theorganoaluminum compound, and optionally 1-hexene can be used in aprecontacting step for a first period of time, and this precontactedmixture then can be contacted with the activator-support to form apostcontacted mixture that can be contacted for a second period of timeprior to initiating the polymerization reaction. For example, the firstperiod of time for contact, the precontact time, between any combinationof the metallocene compound(s), the olefinic monomer (if used), theactivator-support, and the organoaluminum compound can be from about 1minute to about 24 hours, from about 3 minutes to about 1 hour, or fromabout 10 minutes to about 30 minutes. The postcontacted mixtureoptionally can be allowed to remain in contact for a second period oftime, the postcontact time, prior to initiating the polymerizationprocess. According to one aspect of this invention, postcontact timesbetween the precontacted mixture and any remaining catalyst componentscan be from about 1 minute to about 24 hours, or from about 5 minutes toabout 1 hour.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention can comprise contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer (one or more) under polymerization conditions to produce anolefin polymer, wherein the catalyst composition can comprise catalystcomponent I, catalyst component II (or catalyst component I, catalystcomponent II, catalyst component III), an activator, and an optionalco-catalyst. Catalyst components I, II, and III are discussed herein.For instance, catalyst component I can comprise an unbridged metallocenecompound having formula (I), catalyst component II can comprise abridged metallocene compound having formula (II), and catalyst componentIII can comprise a half-metallocene compound having formula (IIIA) orformula (IIIB).

In accordance with one aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising catalyst componentI, catalyst component II (or catalyst component I, catalyst componentII, catalyst component III), and an activator, wherein the activatorcomprises an activator-support. Activator-supports useful in thepolymerization processes of the present invention are disclosed herein.The catalyst composition, optionally, can further comprise one or morethan one organoaluminum compound or compounds (or other suitableco-catalyst). Thus, a process for polymerizing olefins in the presenceof a catalyst composition can employ a catalyst composition comprisingcatalyst component I, catalyst component II (or catalyst component I,catalyst component II, catalyst component III), an activator-support,and an organoaluminum compound. In some aspects, the activator-supportcan comprise (or consist essentially of, or consist of) fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, and the like, or combinations thereof or alternatively afluorided solid oxide and/or a sulfated solid oxide. In some aspects,the organoaluminum compound can comprise (or consist essentially of, orconsist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising catalyst componentI, catalyst component II (or catalyst component I, catalyst componentII, catalyst component III), an activator-support, and an optionalco-catalyst, wherein the co-catalyst can comprise an aluminoxanecompound, an organoboron or organoborate compound, an ionizing ioniccompound, an organoaluminum compound, an organozinc compound, anorganomagnesium compound, or an organolithium compound, or anycombination thereof. Hence, aspects of this invention are directed to aprocess for polymerizing olefins in the presence of a catalystcomposition, the processes comprising contacting a catalyst compositionwith an olefin monomer and optionally an olefin comonomer (one or more)under polymerization conditions to produce an olefin polymer, and thecatalyst composition can comprise catalyst component I, catalystcomponent II (or catalyst component I, catalyst component II, catalystcomponent III), an activator-support, and an aluminoxane compound;alternatively, catalyst component I, catalyst component II (or catalystcomponent I, catalyst component II, catalyst component III), anactivator-support, and an organoboron or organoborate compound;alternatively, catalyst component I, catalyst component II (or catalystcomponent I, catalyst component II, catalyst component III), anactivator-support, and an ionizing ionic compound; alternatively,catalyst component I, catalyst component II (or catalyst component I,catalyst component II, catalyst component III), an activator-support,and an organoaluminum compound; alternatively, catalyst component I,catalyst component II (or catalyst component I, catalyst component II,catalyst component III), an activator-support, and an organozinccompound; alternatively, catalyst component I, catalyst component II (orcatalyst component I, catalyst component II, catalyst component III), anactivator-support, and an organomagnesium compound; or alternatively,catalyst component I, catalyst component II (or catalyst component I,catalyst component II, catalyst component III), an activator-support,and an organolithium compound. Furthermore, more than one co-catalystcan be employed, e.g., an organoaluminum compound and an aluminoxanecompound, an organoaluminum compound and an ionizing ionic compound,etc.

In accordance with another aspect of the invention, the polymerizationprocess can employ a catalyst composition comprising only one catalystcomponent I metallocene compound, only one catalyst component IImetallocene compound, only one catalyst component III half-metallocenecompound (if present), an activator-support, and an organoaluminumcompound.

In accordance with yet another aspect of the invention, thepolymerization process can employ a catalyst composition comprisingcatalyst component I, catalyst component II (or catalyst component I,catalyst component II, catalyst component III), and an activator,wherein the activator comprises an aluminoxane compound, an organoboronor organoborate compound, an ionizing ionic compound, or combinationsthereof.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include those that can be referred to as a batch reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof. Suitable polymerization conditions are used forthe various reactor types. Gas phase reactors can comprise fluidized bedreactors or staged horizontal reactors. Slurry reactors can comprisevertical or horizontal loops. High pressure reactors can compriseautoclave or tubular reactors. Reactor types can include batch orcontinuous processes. Continuous processes can use intermittent orcontinuous product discharge. Processes can also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both. Accordingly, the presentinvention encompasses polymerization reactor systems comprising a singlereactor, comprising two reactors, and comprising more than two reactors.The polymerization reactor system can comprise a slurry reactor, agas-phase reactor, a solution reactor, in certain aspects of thisinvention, as well as multi-reactor combinations thereof.

According to one aspect of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under polymerization conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor system can comprise at least one gas phase reactor. Such systemscan employ a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream can bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product can be withdrawn from the reactor andnew or fresh monomer can be added to replace the polymerized monomer.Such gas phase reactors can comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor system can comprise a solution polymerization reactor whereinthe monomer (and comonomer, if used) are contacted with the catalystcomposition by suitable stirring or other means. A carrier comprising aninert organic diluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention canfurther comprise any combination of at least one raw material feedsystem, at least one feed system for catalyst or catalyst components,and/or at least one polymer recovery system. Suitable reactor systemsfor the present invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 120° C.,depending upon the type of polymerization reactor(s). In some reactorsystems, the polymerization temperature generally can fall within arange from about 70° C. to about 100° C., or from about 75° C. to about95° C. Various polymerization conditions can be held substantiallyconstant, for example, for the production of a particular grade ofolefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). Pressure forgas phase polymerization is usually at about 200 to 500 psig (1.4 MPa to3.4 MPa). High pressure polymerization in tubular or autoclave reactorsis generally run at about 20,000 to 75,000 psig (138 to 517 MPa).Polymerization reactors can also be operated in a supercritical regionoccurring at generally higher temperatures and pressures. Operationabove the critical point of a pressure/temperature diagram(supercritical phase) may offer advantages.

Aspects of this invention are directed to olefin polymerizationprocesses comprising contacting a catalyst composition with an olefinmonomer and an optional olefin comonomer under polymerization conditionsto produce an olefin polymer. The olefin polymer (e.g., ethylenecopolymer) produced by the process can have any of the polymerproperties disclosed herein, for example, a density from about 0.930 toabout 0.948 g/cm³, and/or a zero-shear viscosity greater than about5×10⁵ Pa-sec (at 190° C.), and/or a CY-a parameter in a range from about0.01 to about 0.40 (at 190° C.), and/or a peak molecular weight (Mp) ina range from about 30,000 to about 130,000 g/mol, and/or a reversecomonomer distribution, and/or a single point notched constant tensileload (SP-NCTL) of at least 6,500 hours, and/or a natural draw ratio(NDR) of less than or equal to about 525%, and/or a relationship betweennatural draw ratio (NDR, %) and density (g/cm³) defined by the equation,NDR<7800(density)−6800, and/or a relationship between natural draw ratio(NDR, %) and density (g/cm³) defined by the equation,NDR<13404(density)−12050.

Aspects of this invention also are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the catalystcomposition can comprise catalyst component I, catalyst component II (orcatalyst component I, catalyst component II, catalyst component III), anactivator, and an optional co-catalyst, and wherein the polymerizationprocess is conducted in the absence of added hydrogen (no hydrogen isadded to the polymerization reactor system). As one of ordinary skill inthe art would recognize, hydrogen can be generated in-situ bymetallocene catalyst compositions in various olefin polymerizationprocesses, and the amount generated can vary depending upon the specificcatalyst composition and metallocene compound(s) employed, the type ofpolymerization process used, the polymerization reaction conditionsutilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition with an olefin monomer andoptionally an olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises catalyst component I, catalyst componentII (or catalyst component I, catalyst component II, catalyst componentIII), an activator, and an optional co-catalyst, and wherein thepolymerization process is conducted in the presence of added hydrogen(hydrogen is added to the polymerization reactor system). For example,the ratio of hydrogen to the olefin monomer in the polymerizationprocess can be controlled, often by the feed ratio of hydrogen to theolefin monomer entering the reactor. The added hydrogen to olefinmonomer ratio in the process can be controlled at a weight ratio whichfalls within a range from about 25 ppm to about 1500 ppm, from about 50to about 1000 ppm, or from about 100 ppm to about 750 ppm.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymersproduced by any of the polymerization processes disclosed herein.Articles of manufacture can be formed from, and/or can comprise, thepolymers produced in accordance with this invention.

Polymers and Articles

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and comonomer(s) described herein. For example, theolefin polymer can comprise an ethylene homopolymer, a propylenehomopolymer, an ethylene copolymer (e.g., ethylene/α-olefin,ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including combinations thereof. In one aspect, the olefinpolymer can be an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/1-octene copolymer, while in another aspect,the olefin polymer can be an ethylene/1-hexene copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the ethylene polymers of this invention, whose typicalproperties are provided below.

An illustrative and non-limiting example of an ethylene polymer of thepresent invention can have a density from about 0.930 to about 0.948g/cm³, a zero-shear viscosity greater than about 5×10⁵ Pa-sec (at 190°C.), a CY-a parameter in a range from about 0.01 to about 0.40 (at 190°C.), a peak molecular weight (Mp) in a range from about 30,000 to about130,000 g/mol, and a reverse comonomer distribution. Anotherillustrative and non-limiting example of an ethylene polymer of thepresent invention can have a density from about 0.930 to about 0.948g/cm³, a single point notched constant tensile load (SP-NCTL) of atleast 6,500 hours, and a natural draw ratio (NDR) of less than or equalto about 525%. Yet another illustrative and non-limiting example of anethylene polymer of the present invention can have a density from about0.930 to about 0.948 g/cm³, and a relationship between natural drawratio (NDR, %) and density (g/cm³) defined by the equation,NDR<7800(density)−6800, and/or by the equation,NDR<13404(density)−12050. These illustrative and non-limiting examplesof ethylene polymers consistent with the present invention also can haveany of the polymer properties listed below and in any combination.

Polymers of ethylene (copolymers, terpolymers, etc.) produced inaccordance with some aspects of this invention generally can have a meltindex (MI) from 0 to about 10 g/10 min. Melt indices in the range from 0to about 5 g/10 min, from 0 to about 2 g/10 min, or from 0 to about 1g/10 min, are contemplated in other aspects of this invention. Forexample, a polymer of the present invention can have a melt index in arange from 0 to about 1.5, from 0 to about 0.5, from about 0.01 to about5, from about 0.01 to about 2, from about 0.05 to about 2, from about0.05 to about 1, or from about 0.1 to about 1 g/10 min.

The densities of ethylene-based polymers produced using the catalystsystems and processes disclosed herein often are greater than or equalto about 0.930 g/cm³. In one aspect of this invention, the density ofthe ethylene polymer can be in a range from about 0.930 to about 0.948g/cm³. Yet, in another aspect, the density can be in a range from about0.933 to about 0.948 g/cm³, such as, for example, from about 0.933 toabout 0.946, from about 0.935 to about 0.947, from about 0.935 to about0.946, from about 0.935 to about 0.944, or from about 0.936 to about0.944 g/cm³.

Generally, polymers produced in aspects of the present invention havelow levels of long chain branching, with typically less than about 0.01long chain branches (LCB) per 1000 total carbon atoms, but greater thanzero, and similar in LCB content to polymers shown, for example, in U.S.Pat. Nos. 7,517,939, 8,114,946, and 8,383,754, which are incorporatedherein by reference in their entirety. In some aspects, the number ofLCB per 1000 total carbon atoms can be less than about 0.008, less thanabout 0.007, less than about 0.005, or less than about 0.003 LCB per1000 total carbon atoms. Long chain branches (LCB) per 1000 total carbonatoms can be determined as described in U.S. Pat. No. 8,114,946;“Diagnosing Long-Chain Branching in Polyethylenes,” J. Mol. Struct.485-486, 569-584 (1999); Y. Yu, D. C. Rohlfing, G. R. Hawley, and P. J.DesLauriers, Polymer Preprint, 44, 50, (2003); and J. Phys. Chem. 1980,84, 649; the disclosures of which are incorporated herein by referencein their entirety.

Consistent with aspects of this disclosure, ethylene polymers can have asingle point notched constant tensile load (SP-NCTL) of at least 6,500hours. Moreover, in some aspects, the ethylene polymers described hereincan have a single point notched constant tensile load (SP-NCTL) of atleast 7,000 hours, at least 7,500 hours, at least 8,000 hours, at least8,500 hours, at least 9,000 hours, or at least 10,000 hours, and oftencan range as high as 15,000 to 20,000 hours. The test is typicallystopped after a certain number of hours is reached, and given the longduration of the test, the upper limit of SP-NCTL (in hours) is generallynot determined.

Often, the ethylene polymers can have a natural draw ratio (NDR) of lessthan or equal to about 525%, less than or equal to about 520%, less thanor equal to about 510%, or less than or equal to about 500%.Representative non-limiting ranges include the following: from about 400to about 525%, from about 400 to about 515%, from about 420 to about520%, from about 430 to about 515%, and the like. In these and otheraspects, ethylene polymers disclosed herein can have a relationshipbetween natural draw ratio (NDR, %) and density (g/cm³) defined by theequation, NDR<7800(density)−6800; alternatively, NDR<7800(density)−6820;alternatively, NDR<7800(density)−6840; alternatively,NDR<13404(density)−12050; alternatively, NDR<13404(density)−12070; oralternatively, NDR<13404(density)−12090.

In some aspects, the ethylene polymers of this invention can have a PSP2value in a range from about 7.5 to about 15, or from about 8 to about14. In other aspects, the PSP2 value can be in a range from about 8.5 toabout 13, or from about 9 to about 12.5. PSP2 refers to the PrimaryStructure Parameter 2 as described and determined in U.S. Pat. No.8,048,679, the disclosure of which is incorporated herein by referencein its entirety.

Ethylene copolymers, for example, produced using the polymerizationprocesses and catalyst systems described hereinabove can, in someaspects, have a reverse comonomer distribution, generally, the highermolecular weight components of the polymer have higher comonomerincorporation than the lower molecular weight components. Typically,there is increasing comonomer incorporation with increasing molecularweight. In one aspect, the number of short chain branches (SCB) per 1000total carbon atoms of the polymer can be greater at Mw than at Mn. Inanother aspect, the number of SCB per 1000 total carbon atoms of thepolymer can be greater at Mz than at Mw. In yet another aspect, thenumber of SCB per 1000 total carbon atoms of the polymer can be greaterat Mz than at Mn. In still another aspect, the number of SCB per 1000total carbon atoms of the polymer at a molecular weight of 10⁶ can begreater than at a molecular weight of 10⁵.

Ethylene polymers, such as homopolymers, copolymers, etc., consistentwith various aspects of the present invention generally can have a peakmolecular weight (Mp), for instance, in a range from about 30,000 toabout 130,000, from about 35,000 to about 120,000, from about 35,000 toabout 100,000, from about 40,000 to about 110,000, from about 40,000 toabout 95,000, from about 50,000 to about 120,000, from about 50,000 toabout 100,000, from about 30,000 to about 90,000, or from about 40,000to about 80,000 g/mol.

In an aspect, ethylene polymers described herein can have a high loadmelt index (HLMI) in a range from about 1 to about 20, from about 2 toabout 20, from about 4 to about 15, or from about 5 to about 18 g/10min. In another aspect, ethylene polymers described herein can have aHLMI in a range from 0 to about 50, from 0 to about 40, from about 0.1to about 45, or from about 5 to about 40 g/10 min.

In an aspect, ethylene polymers described herein can have a ratio ofMw/Mn, or the polydispersity index, in a range from about 5 to about 25,from about 7 to about 22, from about 7 to about 20, from about 8 toabout 20, from about 8 to about 18, or from about 9 to about 18. Inanother aspect, ethylene polymers described herein can have a Mw/Mn in arange from about 10 to about 50, from about 11 to about 48, from about10 to about 45, or from about 12 to about 30.

In an aspect, ethylene polymers described herein can have a ratio ofMz/Mw in a range from about 4.5 to about 7.5, from about 4.5 to about6.5, from about 4.8 to about 7, from about 4.8 to about 6.2, from about5 to about 6.5, or from about 5 to about 6. In another aspect, ethylenepolymers described herein can have a Mz/Mw in a range from about 2.4 toabout 8, from about 2.4 to about 7, from about 2.5 to about 7.5, or fromabout 2.5 to about 6.

In an aspect, ethylene polymers described herein can have aweight-average molecular weight (Mw) in a range from about 200,000 toabout 500,000, from about 200,000 to about 425,000, from about 210,000to about 475,000, from about 210,000 to about 400,000, from about225,000 to about 450,000, or from about 225,000 to about 375,000 g/mol.In another aspect, ethylene polymers described herein can have a Mw in arange from about 150,000 to about 600,000, from about 150,000 to about550,000, or from about 175,000 to about 375,000 g/mol.

In an aspect, ethylene polymers described herein can have anumber-average molecular weight (Mn) in a range from about 8,000 toabout 60,000, from about 8,000 to about 35,000, from about 15,000 toabout 55,000, from about 15,000 to about 30,000, from about 18,000 toabout 50,000, or from about 18,000 to about 28,000 g/mol. In anotheraspect, ethylene polymers described herein can have a Mn in a range fromabout 5,000 to about 30,000, from about 5,000 to about 25,000, fromabout 5,000 to about 17,000, from about 5,000 to about 15,000, or fromabout 6,000 to about 12,000 g/mol.

In an aspect, ethylene polymers described herein can have a z-averagemolecular weight (Mz) in a range from about 1,000,000 to about5,000,000, from about 1,000,000 to about 3,000,000, from about 1,100,000to about 4,000,000, from about 1,100,000 to about 2,500,000, from about1,200,000 to about 3,000,000, or from about 1,200,000 to about 2,000,000g/mol. In another aspect, ethylene polymers described herein can have aMz in a range from about 450,000 to about 4,000,000, from about 450,000to about 3,000,000, from about 520,000 to about 2,500,000, or from about500,000 to about 800,000 g/mol.

In an aspect, ethylene polymers described herein can have a CY-aparameter at 190° C. in a range from about 0.01 to about 0.40, fromabout 0.03 to about 0.30, from about 0.05 to about 0.25, from about 0.08to about 0.35, or from about 0.08 to about 0.28. In another aspect,ethylene polymers described herein can have a CY-a parameter in a rangefrom about 0.40 to about 0.60, from about 0.45 to about 0.58, or fromabout 0.50 to about 0.56.

In an aspect, ethylene polymers described herein can have a zero-shearviscosity at 190° C. of greater than or equal to about 5×10⁵, greaterthan or equal to about 7.5×10⁵, greater than or equal to about 1×10⁶, ina range from about 5×10⁵ to about 1×10¹², in a range from about 1×10⁶ toabout 1×10⁹, or in a range from about 1×10⁶ to about 5×10⁸ Pa-sec. Inanother aspect, ethylene polymers described herein can have a zero-shearviscosity in a range from about 1×10⁴ to about 1×10⁹, from about 1×10⁴to about 1×10⁸, or from about 1×10⁴ to about 5×10⁶ Pa-sec.

Ethylene polymers consistent with certain aspects of the invention oftencan have a bimodal molecular weight distribution (as determined usinggel permeation chromatography (GPC) or other recognized analyticaltechnique). Often, in a bimodal molecular weight distribution, there isa valley between the peaks, and the peaks can be separated ordeconvoluted. Typically, a bimodal molecular weight distribution can becharacterized as having an identifiable high molecular weight component(or distribution) and an identifiable low molecular weight component (ordistribution).

Polymers of ethylene, whether homopolymers, copolymers, and so forth,can be formed into various articles of manufacture. Articles which cancomprise polymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes. Suchprocesses and materials are described in Modern Plastics Encyclopedia,Mid-November 1995 Issue, Vol. 72, No. 12; and Film ExtrusionManual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a catalyst composition with an olefin monomerand an optional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer, wherein thecatalyst composition can comprise catalyst component I, catalystcomponent II, optional catalyst component III, an activator (e.g., anactivator-support comprising a solid oxide treated with anelectron-withdrawing anion), and an optional co-catalyst (e.g., anorganoaluminum compound); and (ii) forming an article of manufacturecomprising the olefin polymer. The forming step can comprise blending,melt processing, extruding, molding, or thermoforming, and the like,including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight, and high load melt index (HLMI,g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight. Polymer density was determined in grams per cubiccentimeter (g/cm³) on a compression molded sample, cooled at about 15°C. per hour, and conditioned for about 40 hours at room temperature inaccordance with ASTM D1505 and ASTM D1928, procedure C. Natural DrawRatio (NDR, %) was determined in accordance with ASTM D638 (see alsoU.S. Pat. No. 7,589,162, which is incorporated herein by reference inits entirety). Notched tensiles (Single point notched constant tensileload, SP-NCTL, hours), a measure of polymer stress crack resistance,were determined in accordance with ASTM D5397 at 30% yield.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, Mass.) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. The integralcalibration method was used to deduce molecular weights and molecularweight distributions using a Chevron Phillips Chemicals Company's HDPEpolyethylene resin, MARLEX® BHB5003, as the broad standard. The integraltable of the broad standard was pre-determined in a separate experimentwith SEC-MALS. Mn is the number-average molecular weight, Mw is theweight-average molecular weight, Mz is the z-average molecular weight,My is the viscosity-average molecular weight, and Mp is the peakmolecular weight.

Melt rheological characterizations were performed as follows.Small-strain (10%) oscillatory shear measurements were performed on aRheometrics Scientific, Inc. ARES rheometer using parallel-plategeometry. All rheological tests were performed at 190° C. The complexviscosity |η*| versus frequency (ω) data were then curve fitted usingthe modified three parameter Carreau-Yasuda (CY) empirical model toobtain the zero shear viscosity—η₀, characteristic viscous relaxationtime—τ_(η), and the breadth parameter—α. The simplified Carreau-Yasuda(CY) empirical model is as follows:

${{{\eta^{*}(\omega)}} = \frac{\eta_{0}}{\left\lbrack {1 + \left( {\tau_{\eta}\omega} \right)^{a}} \right\rbrack^{{({1 - n})}/a}}},$wherein:

-   -   |η*(ω)|=magnitude of complex shear viscosity;    -   η₀=zero shear viscosity;    -   τ_(η)=viscous relaxation time;    -   α=“breadth” parameter (CY-a parameter);    -   n=fixes the final power law slope, fixed at 2/11; and    -   ω=angular frequency of oscillatory shearing deformation.

Details of the significance and interpretation of the CY model andderived parameters may be found in: C. A. Hieber and H. H. Chiang,Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng.Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong and O. Hasseger,Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition,John Wiley & Sons (1987); each of which is incorporated herein byreference in its entirety.

Short chain branch content and short chain branching distribution (SCBD)across the molecular weight distribution were determined via anIR5-detected GPC system (IR5-GPC), wherein the GPC system was a PL220GPC/SEC system (Polymer Labs, an Agilent company) equipped with threeStyragel HMW-6E columns (Waters, Mass.) for polymer separation. Athermoelectric-cooled IR5 MCT detector (IR5) (Polymer Char, Spain) wasconnected to the GPC columns via a hot-transfer line. Chromatographicdata were obtained from two output ports of the IR5 detector. First, theanalog signal goes from the analog output port to a digitizer beforeconnecting to Computer “A” for molecular weight determinations via theCirrus software (Polymer Labs, now an Agilent Company) and the integralcalibration method using a broad MWD HDPE Marlex™ BHB5003 resin (ChevronPhillips Chemical) as the broad molecular weight standard. The digitalsignals, on the other hand, go via a USB cable directly to Computer “B”where they are collected by a LabView data collection software providedby Polymer Char. Chromatographic conditions were set as follows: columnoven temperature of 145° C.; flowrate of 1 mL/min; injection volume of0.4 mL; and polymer concentration of about 2 mg/mL, depending on samplemolecular weight. The temperatures for both the hot-transfer line andIR5 detector sample cell were set at 150° C., while the temperature ofthe electronics of the IR5 detector was set at 60° C. Short chainbranching content was determined via an in-house method using theintensity ratio of CH₃ (I_(CH3)) to CH₂ (I_(CH2)) coupled with acalibration curve. The calibration curve was a plot of SCB content(x_(SCB)) as a function of the intensity ratio of I_(CH3)/I_(CH2). Toobtain a calibration curve, a group of polyethylene resins (no less than5) of SCB level ranging from zero to ca. 32 SCB/1,000 total carbons (SCBStandards) were used. All these SCB Standards have known SCB levels andflat SCBD profiles pre-determined separately by NMR and thesolvent-gradient fractionation coupled with NMR (SGF-NMR) methods. UsingSCB calibration curves thus established, profiles of short chainbranching distribution across the molecular weight distribution wereobtained for resins fractionated by the IR5-GPC system under exactly thesame chromatographic conditions as for these SCB standards. Arelationship between the intensity ratio and the elution volume wasconverted into SCB distribution as a function of MWD using apredetermined SCB calibration curve (i.e., intensity ratio ofI_(CH3)/I_(CH2) vs. SCB content) and MW calibration curve (i.e.,molecular weight vs. elution time) to convert the intensity ratio ofI_(CH3)/I_(CH2) and the elution time into SCB content and the molecularweight, respectively.

Fluorided silica-coated alumina activator-supports used in Examples 7-12were prepared as follows. Bohemite was obtained from W.R. Grace &Company under the designation “Alumina A” and having a surface area ofabout 300 m²/g, a pore volume of about 1.3 mL/g, and an average particlesize of about 100 microns. The alumina was first calcined in dry air atabout 600° C. for approximately 6 hours, cooled to ambient temperature,and then contacted with tetraethylorthosilicate in isopropanol to equal25 wt. % SiO₂. After drying, the silica-coated alumina was calcined at600° C. for 3 hours. Fluorided silica-coated alumina (7 wt. % F) wasprepared by impregnating the calcined silica-coated alumina with anammonium bifluoride solution in methanol, drying, and then calcining for3 hours at 600° C. in dry air. Afterward, the fluorided silica-coatedalumina was collected and stored under dry nitrogen, and was usedwithout exposure to the atmosphere.

Sulfated alumina activator-supports used in Examples 13-25 were preparedas follows. Bohemite was obtained from W.R. Grace & Company under thedesignation “Alumina A” and having a surface area of about 300 m²/g anda pore volume of about 1.3 mL/g. This material was obtained as a powderhaving an average particle size of about 100 microns. This material wasimpregnated to incipient wetness with an aqueous solution of ammoniumsulfate to equal about 15% sulfate. This mixture was then placed in aflat pan and allowed to dry under vacuum at approximately 110° C. forabout 16 hours. To calcine the resultant powdered mixture, the materialwas fluidized in a stream of dry air at about 550° C. for about 6 hours.Afterward, the sulfated alumina was collected and stored under drynitrogen, and was used without exposure to the atmosphere.

Examples 1-25

Examples 1-6 utilized a commercially-available, nominal 0.937 density,ethylene/1-hexene copolymer (Chevron Phillips Chemical Company LP)produced using a chromium-based catalyst system. The followingmetallocene compounds were used in Examples 7-25 (Ph=phenyl,t-Bu=tert-butyl; py=pyridine):

The polymerization experiments of Examples 7-12 were conducted in aone-gallon stainless steel reactor. Isobutane (1.8-2.0 L) was used inall runs. Metallocene solutions were prepared at about 1 mg/mL intoluene. Approximately 0.6 mmol of alkyl aluminum (triisobutylaluminum,TIBA), 300 mg of fluorided silica-coated alumina, and the metallocenesolutions were added in that order through a charge port while slowlyventing isobutane vapor. The charge port was closed and isobutane wasadded. The contents of the reactor were stirred and heated to thedesired run temperature of about 90° C., and ethylene was thenintroduced into the reactor with 1-hexene and hydrogen at a specific ppmby weight of the ethylene. Ethylene and hydrogen were fed on demand atthe specified weight ratio to maintain the target pressure of 390 psigpressure for the 30-60 minute length of the polymerization run (targetwas a nominal 400 g of polymer produced). The reactor was maintained atthe desired run temperature throughout the run by an automatedheating-cooling system. Table I summarizes certain information relatingto the polymerization experiments of Examples 7-12.

TABLE I Examples 7-12. MET-A MET-B 1-hexene H₂ PE produced Example (mg)(mg) (g) (ppm) (g) 7 1 1.5 10 150 403 8 1 1.5 15 150 416 9 0.9 1.5 15150 399 10 0.9 1.5 20 150 412 11 0.8 1.5 15 175 337 12 1 1.7 30 150 406

Example 13 used the same general procedure as in Examples 7-12, exceptthat sulfated alumina was used, a 25 wt. % solution of TIBA was used,and the hydrogen addition was measured as the pressure drop (ΔP) from anauxiliary vessel with a 700 psig starting pressure. For Example 13, 0.5mL of TIBA, 0.15 g of sulfated alumina, 1 mL of MET-D solution, 0.4 mLof MET-C solution, and 42 g of 1-hexene were used. The reactiontemperature was 78° C., the reactor pressure was 345 psig, the reactiontime was 30 min, and ΔP was 94 psig; 332 g of polymer were produced.Examples 14-21 were conducted similarly to that of Example 13, with thedifferences noted as follows:

For Example 14, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 1 mL of MET-Asolution, 0.25 mL of MET-C solution, and 42 g of 1-hexene were used. Thereaction temperature was 78° C., the reactor pressure was 345 psig, thereaction time was 30 min, and ΔP was 63 psig; 273 g of polymer wereproduced.

For Example 15, 0.5 mL of TIBA, 0.15 g of sulfated alumina, 1 mL ofMET-D solution, 0.4 mL of MET-C solution, and 42 g of 1-hexene wereused. The reaction temperature was 78° C., the reactor pressure was 345psig, the reaction time was 30 min, and ΔP was 63 psig; 309 g of polymerwere produced.

For Example 16, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 1 mL of MET-Asolution, 0.3 mL of MET-C solution, and 30 g of 1-hexene were used. Thereaction temperature was 78° C., the reactor pressure was 345 psig, thereaction time was 30 min, and ΔP was 40 psig; 264 g of polymer wereproduced.

For Example 17, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 0.1 mL ofMET-A solution, 1 mL of MET-C solution, 0.2 mL of MET-E solution, and 10g of 1-hexene were used. The reaction temperature was 85° C., thereactor pressure was 374 psig, the reaction time was 30 min, and ΔP was63 psig; 346 g of polymer were produced.

For Example 18, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 0.2 mL ofMET-A solution, 1 mL of MET-C solution, 0.5 mL of MET-E solution, and 15g of 1-hexene were used. The reaction temperature was 85° C., thereactor pressure was 374 psig, the reaction time was 30 min, and ΔP was63 psig; 376 g of polymer were produced.

For Example 19, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 0.2 mL ofMET-A solution, 1 mL of MET-C solution, 1 mL of MET-E solution, and 20 gof 1-hexene were used. The reaction temperature was 85° C., the reactorpressure was 374 psig, the reaction time was 30 min, and ΔP was 63 psig;328 g of polymer were produced.

For Example 20, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 0.5 mL ofMET-A solution, 1 mL of MET-C solution, 0.2 mL of MET-F solution, and 10g of 1-hexene were used. The reaction temperature was 85° C., thereactor pressure was 374 psig, the reaction time was 30 min, and ΔP was24 psig; 229 g of polymer were produced.

For Example 21, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 0.5 mL ofMET-A solution, 0.5 mL of MET-C solution, 0.5 mL of MET-F solution, and40 g of 1-hexene were used. The reaction temperature was 80° C., thereactor pressure was 374 psig, the reaction time was 30 min, and ΔP was95 psig; 249 g of polymer were produced.

For Example 22, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 0.4 mL ofMET-C solution, 1 mL of MET-D solution, and 42 g of 1-hexene were used.The reaction temperature was 78° C., the reactor pressure was 345 psig,the reaction time was 30 min, and ΔP was 63 psig; 309 g of polymer wereproduced.

For Example 23, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 1 mL of MET-Asolution, 0.2 mL of MET-C solution, 0.1 mL of MET-E solution, and 45 gof 1-hexene were used. The reaction temperature was 85° C., the reactorpressure was 374 psig, the reaction time was 30 min, and ΔP was 42 psig;188 g of polymer were produced.

For Example 24, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 1 mL of MET-Csolution, 0.2 mL of MET-E solution, and 20 g of 1-hexene were used. Thereaction temperature was 85° C., the reactor pressure was 374 psig, thereaction time was 30 min, and ΔP was 63 psig; 442 g of polymer wereproduced.

For Example 25, 0.5 mL of TIBA, 0.2 g of sulfated alumina, 0.2 mL ofMET-C solution, 1 mL of MET-D solution, 0.3 mL of MET-E solution, and 45g of 1-hexene were used. The reaction temperature was 85° C., thereactor pressure was 374 psig, the reaction time was 30 min, and ΔP was42 psig; 163 g of polymer were produced.

Table II summarizes certain polymer properties of Examples 1-25, whileFIGS. 1-3 illustrate the short chain branch distributions (comonomerdistributions) of certain polymers, FIGS. 4-8 illustrate the dynamicrheology properties at 190° C. for certain polymers, FIGS. 9-13illustrate the molecular weight distributions (amount of polymer versusthe logarithm of molecular weight) of certain polymers, and FIGS. 14-15illustrate the natural draw ratio versus the density for certainpolymers.

As shown in FIGS. 2-3, polymers produced using certain metallocene-basedcatalyst systems disclosed herein had a reverse comonomer distribution(e.g., relatively more short chain branches (SCB) at the highermolecular weights; assumes 2 methyl chain ends (CE)), as contrasted withthe standard comonomer distribution resulting from a chromium-basedcatalyst system (see FIG. 1). For instance, in FIGS. 2-3, the number ofSCB per 1000 total carbon (TC) atoms of the polymer at Mz (or Mw) isgreater than at Mn, while such is not the case in FIG. 1.

The rheology characteristics in Table II (e.g., zero-shear viscosity,CY-a parameter) and the viscosity curves of FIGS. 4-8 illustrate a rangeof improved processability of polymers produced using certainmetallocene-based catalyst systems disclosed herein, as compared tothose produced from a chromium-based catalyst system. For instance, bycomparing the shape of the viscosity curve and the zero-shear viscosityvalues, metallocene-based polymers, surprisingly, were produced whichwould likely have equivalent or superior melt strength to those of thechromium-based polymers; see e.g., FIGS. 4-6 and Examples 1 and 7-12.Polymers with improved extrusion processability also were produced; seee.g., FIGS. 7-8.

Metallocene-based polymers were produced having similar or broadermolecular weight distributions to chromium-based polymers, and a widerange of Mn, Mw, Mp, and Mz parameters; see e.g., FIGS. 9-13 andExamples 1 and 7-25.

The NDR data in Table II and FIGS. 14-15 demonstrate superior NDRperformance for the metallocene-based polymers, as compared to thechromium-based polymers: e.g., lower NDR values at an equivalentdensity, the same or lower NDR values at a higher density, etc. LowerNDR values typically correlate with improved stress crack resistance ofthe polymer.

Also unexpectedly, the metallocene-based polymers provided significantlyimproved stress crack resistance, as measured by the notched tensiles.Examples 1-6 failed the notched tensiles test at an average of 3,025hours (and with an average 0.9377 density), while Examples 8-11 did notfail the notched tensile test at over 10,000 hours (in excess of 1 yearof testing). Moreover, Examples 8-11 had a significantly higher averagedensity of 0.9435 g/cc. Accordingly, polymers were produced that had aunique combination of chromium-like processability and melt strength,improved stress crack resistance (e.g., higher notched tensiles, lowerNDR), and a higher density.

TABLE II Polymer Properties of Examples 1-25. HLMI Density NDR Mn Mw MzMv Mp Example (g/10 min) (g/cc) (%) (kg/mol) (kg/mol) (kg/mol) (kg/mol)(kg/mol) Mw/Mn  1 12 0.937 525 16.5 197 1177 149 73 11.9  2 16 0.938  317 0.938  4 13 0.937 537  5 14 0.938 533  6 13 0.938 532  7 12 0.9479546 18.8 252 1384 181 50 13.4  8 15 0.9446 506 22.2 247 1334 177 47 11.1 9 12 0.9445 520 22.2 256 1373 185 49 11.5 10 14 0.9419 473 19.0 2461318 177 43 12.9 11 7 0.9431 462 19.9 351 1828 250 47 17.7 12 11 0.9375468 25.0 258 1533 187 62 10.3 13 42 0.9423 432 5.9 181 682 132 8 30.4 1439 0.9422 425 10.3 191 808 140 19 18.6 15 32 0.9413 407 7.8 209 807 154433 27.0 16 7 0.9386 401 8.3 235 748 184 384 28.2 17 21 0.9426 540 14.3172 672 137 78 12.0 18 13 0.9367 453 13.6 195 703 158 89 14.4 19 170.9379 477 12.0 150 478 124 82 12.5 20 0.4 0.9397 406 11.2 541 2356 415482 48.3 21 11 0.9420 510 8.0 358 2401 246 77 44.5 22 26 0.9400 503 9.2198 798 147 16 21.7 23 2.6 7.8 206 546 170 271 26.3 24 4.4 9.1 221 571185 261 24.3 25 2.5 8.6 198 522 164 264 23.1 SP-NCTL η₀ τ_(η) Example(hr) (Pa-sec) CY-a (sec) PSP2  1 6295 4.4E+06 0.15 1.9E+01  2 1841  33438  4 2144  5 1691  6 2746  7 3012 2.3E+07 0.12 9.9E+01 8.8  8 >109872.2E+07 0.13 2.3E+02  9 >10987 7.4E+06 0.14 5.2E+01 8.8 10 >109873.2E+06 0.17 3.3E+01 10.1 11 >10987 2.6E+06 0.27 3.9E+01 12 >86131.5E+08 0.09 2.2E+02 13 7.4E+04 14 7.2E+04 15 >9547 1.1E+05 0.55 1.2E+0012.4 16 1.2E+05 17 4.3E+04 18 4.1E+04 0.34 1.1E−01 19 2.7E+04 0.356.3E−01 20 5.7E+05 0.48 1.8E+00 21 1.1E+06 0.23 8.4E+00 22 >9692 1.1E+050.51 1.1E+00 11.9 23 7.7E+04 0.53 3.2E−01 24 7.9E+04 0.53 3.0E−01 256.8E+04 0.53 2.6E−01

The invention is described above with reference to numerous aspects andembodiments, and specific examples. Many variations will suggestthemselves to those skilled in the art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims. Other embodiments of the invention caninclude, but are not limited to, the following (embodiments aredescribed as “comprising” but, alternatively, can “consist essentiallyof” or “consist of”):

Embodiment 1

An ethylene polymer having a density from about 0.930 to about 0.948g/cm³, a zero-shear viscosity greater than about 5×10⁵ Pa-sec, a CY-aparameter in a range from about 0.01 to about 0.40, a peak molecularweight (Mp) in a range from about 30,000 to about 130,000 g/mol, and areverse comonomer distribution.

Embodiment 2

An ethylene polymer having a density from about 0.930 to about 0.948g/cm³, a single point notched constant tensile load (SP-NCTL) of atleast 6,500 hours, and a natural draw ratio (NDR) of less than or equalto about 525%.

Embodiment 3

An ethylene polymer having a density from about 0.930 to about 0.948g/cm³, and a relationship between natural draw ratio (NDR, %) anddensity (g/cm³) defined by one or more of the following equations:NDR<7800(density)−6800, NDR<7800(density)−6820, NDR<7800(density)−6840,NDR<13404(density)−12050, NDR<13404(density)−12070, and/orNDR<13404(density)−12090.

Embodiment 4

The polymer defined in any one of embodiments 1-3, wherein the ethylenepolymer has a melt index in any range disclosed herein, e.g., from 0 toabout 2, from 0 to about 1, from 0 to about 0.5 g/10 min, etc.

Embodiment 5

The polymer defined in any one of embodiments 1-4, wherein the ethylenepolymer has a density in any range disclosed herein, e.g., from about0.933 to about 0.948, from about 0.933 to about 0.946, from about 0.935to about 0.947, from about 0.935 to about 0.944, from about 0.936 toabout 0.944 g/cm³, etc.

Embodiment 6

The polymer defined in any one of embodiments 1-5, wherein the ethylenepolymer has less than about 0.008 long chain branches (LCB) per 1000total carbon atoms, e.g., less than about 0.005 LCB, less than about0.003 LCB, etc.

Embodiment 7

The polymer defined in any one of embodiments 1-6, wherein the ethylenepolymer has a single point notched constant tensile load (SP-NCTL) inany range disclosed herein, e.g., at least 7,000 hours, at least 7,500hours, at least 8,000 hours, at least 8,500 hours, at least 9,000 hours,at least 10,000 hours, etc.

Embodiment 8

The polymer defined in any one of embodiments 1-7, wherein the ethylenepolymer has a natural draw ratio (NDR) in any range disclosed herein,e.g., less than or equal to about 520%, less than or equal to about510%, in a range from about 400 to about 525%, in a range from about 420to about 520%, in a range from about 430 to about 515%, etc.

Embodiment 9

The polymer defined in any one of embodiments 1-8, wherein the ethylenepolymer has a PSP2 in any range disclosed herein, e.g., from about 7.5to about 15, from about 8 to about 14, from about 8.5 to about 13, fromabout 9 to about 12.5, etc.

Embodiment 10

The polymer defined in any one of embodiments 1-9, wherein the ethylenepolymer has a reverse comonomer distribution, e.g., the number of shortchain branches (SCB) per 1000 total carbon atoms of the polymer at Mw isgreater than at Mn, the number of short chain branches (SCB) per 1000total carbon atoms of the polymer at Mz is greater than at Mw, thenumber of SCB per 1000 total carbon atoms of the polymer at Mz isgreater than at Mn, the number of short chain branches (SCB) per 1000total carbon atoms of the polymer at a molecular weight of 10⁶ isgreater than at a molecular weight of 10⁵, etc.

Embodiment 11

The polymer defined in any one of embodiments 1-10, wherein the ethylenepolymer has a Mp in any range disclosed herein, e.g., from about 30,000to about 130,000, from about 35,000 to about 120,000, from about 40,000to about 110,000, from about 40,000 to about 80,000 g/mol, etc.

Embodiment 12

The polymer defined in any one of embodiments 1-11, wherein the ethylenepolymer has a HLMI in any range disclosed herein, e.g., from about 1 toabout 20, from about 2 to about 20, from about 5 to about 18 g/10 min,etc.

Embodiment 13

The polymer defined in any one of embodiments 1-12, wherein the ethylenepolymer has a ratio of Mw/Mn in any range disclosed herein, e.g., fromabout 5 to about 25, from about 7 to about 20, from about 8 to about 18,etc.

Embodiment 14

The polymer defined in any one of embodiments 1-13, wherein the ethylenepolymer has a ratio of Mz/Mw in any range disclosed herein, e.g., fromabout 4.5 to about 7.5, from about 4.8 to about 7, from about 5 to about6, etc.

Embodiment 15

The polymer defined in any one of embodiments 1-14, wherein the ethylenepolymer has a Mw in any range disclosed herein, e.g., from about 200,000to about 500,000, from about 225,000 to about 450,000, from about225,000 to about 375,000 g/mol, etc.

Embodiment 16

The polymer defined in any one of embodiments 1-15, wherein the ethylenepolymer has a Mn in any range disclosed herein, e.g., from about 8,000to about 60,000, from about 15,000 to about 30,000, from about 18,000 toabout 50,000 g/mol, etc.

Embodiment 17

The polymer defined in any one of embodiments 1-16, wherein the ethylenepolymer has a Mz in any range disclosed herein, e.g., from about1,000,000 to about 5,000,000, from about 1,000,000 to about 3,000,000,from about 1,200,000 to about 2,000,000 g/mol, etc.

Embodiment 18

The polymer defined in any one of embodiments 1-17, wherein the ethylenepolymer has a CY-a parameter in any range disclosed herein, e.g., fromabout 0.01 to about 0.40, from about 0.03 to about 0.30, from about 0.08to about 0.35, etc.

Embodiment 19

The polymer defined in any one of embodiments 1-18, wherein the ethylenepolymer has a zero-shear viscosity in any range disclosed herein, e.g.,greater than about 5×10⁵, greater than about 7.5×10⁵, greater than about1×10⁶, in a range from about 1×10⁶ to about 1×10⁹ Pa-sec, etc.

Embodiment 20

The polymer defined in any one of embodiments 1-11, wherein the ethylenepolymer has a HLMI in any range disclosed herein, e.g., from 0 to about50, from about 0.1 to about 45, from about 5 to about 40 g/10 min, etc.

Embodiment 21

The polymer defined in any one of embodiments 1-11 and 20, wherein theethylene polymer has a ratio of Mw/Mn in any range disclosed herein,e.g., from about 10 to about 50, from about 11 to about 48, from about12 to about 30, etc.

Embodiment 22

The polymer defined in any one of embodiments 1-11 and 20-21, whereinthe ethylene polymer has a ratio of Mz/Mw in any range disclosed herein,e.g., from about 2.4 to about 8, from about 2.4 to about 7, from about2.5 to about 6, etc.

Embodiment 23

The polymer defined in any one of embodiments 1-11 and 20-22, whereinthe ethylene polymer has a Mw in any range disclosed herein, e.g., fromabout 150,000 to about 600,000, from about 150,000 to about 550,000,from about 175,000 to about 375,000 g/mol, etc.

Embodiment 24

The polymer defined in any one of embodiments 1-11 and 20-23, whereinthe ethylene polymer has a Mn in any range disclosed herein, e.g., fromabout 5,000 to about 17,000, from about 5,000 to about 15,000, fromabout 6,000 to about 12,000 g/mol, etc.

Embodiment 25

The polymer defined in any one of embodiments 1-11 and 20-24, whereinthe ethylene polymer has a Mz in any range disclosed herein, e.g., fromabout 450,000 to about 3,000,000, from about 520,000 to about 2,500,000,from about 500,000 to about 800,000 g/mol, etc.

Embodiment 26

The polymer defined in any one of embodiments 2-11 and 20-25, whereinthe ethylene polymer has a CY-a parameter in any range disclosed herein,e.g., from about 0.40 to about 0.60, from about 0.45 to about 0.58, fromabout 0.50 to about 0.56, etc.

Embodiment 27

The polymer defined in any one of embodiments 2-11 and 20-26, whereinthe ethylene polymer has a zero-shear viscosity in any range disclosedherein, e.g., from about 1×10⁴ to about 1×10⁹, from about 1×10⁴ to about1×10⁸, from about 1×10⁴ to about 5×10⁶ Pa-sec, etc.

Embodiment 28

The polymer defined in any one of embodiments 1-27, wherein the ethylenepolymer is an ethylene/α-olefin copolymer.

Embodiment 29

The polymer defined in any one of embodiments 1-28, wherein the ethylenepolymer is an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/1-octene copolymer.

Embodiment 30

The polymer defined in any one of embodiments 1-29, wherein the ethylenepolymer is an ethylene/1-hexene copolymer.

Embodiment 31

An article comprising the ethylene polymer defined in any one ofembodiments 1-30.

Embodiment 32

An article comprising the ethylene polymer defined in any one ofembodiments 1-30, wherein the article is an agricultural film, anautomobile part, a bottle, a drum, a fiber or fabric, a food packagingfilm or container, a food service article, a fuel tank, a geomembrane, ahousehold container, a liner, a molded product, a medical device ormaterial, a pipe, a sheet or tape, or a toy.

Embodiment 33

A catalyst composition comprising: catalyst component I comprising anyunbridged metallocene compound disclosed herein, catalyst component IIcomprising any bridged metallocene compound disclosed herein, anyactivator disclosed herein, and optionally, any co-catalyst disclosedherein.

Embodiment 34

The composition defined in embodiment 33, wherein catalyst component IIcomprises a bridged zirconium or hafnium based metallocene compound.

Embodiment 35

The composition defined in embodiment 33, wherein catalyst component IIcomprises a bridged zirconium or hafnium based metallocene compound withan alkenyl substituent.

Embodiment 36

The composition defined in embodiment 33, wherein catalyst component IIcomprises a bridged zirconium or hafnium based metallocene compound withan alkenyl substituent and a fluorenyl group.

Embodiment 37

The composition defined in embodiment 33, wherein catalyst component IIcomprises a bridged zirconium or hafnium based metallocene compound witha cyclopentadienyl group and a fluorenyl group, and with an alkenylsubstituent on the bridging group and/or on the cyclopentadienyl group.

Embodiment 38

The composition defined in embodiment 33, wherein catalyst component IIcomprises a bridged metallocene compound having an aryl groupsubstituent on the bridging group.

Embodiment 39

The composition defined in embodiment 33, wherein catalyst component IIcomprises a dinuclear bridged metallocene compound with an alkenyllinking group.

Embodiment 40

The composition defined in embodiment 33, wherein catalyst component IIcomprises a bridged metallocene compound having formula (II):

wherein M is any Group IV transition metal disclosed herein, Cp is anycyclopentadienyl, indenyl, or fluorenyl group disclosed herein, each Xindependently is any monoanionic ligand disclosed herein, R^(X) andR^(Y) independently are any substituent disclosed herein, and E is anybridging group disclosed herein.

Embodiment 41

The composition defined in any one of embodiments 33-40, whereincatalyst component I comprises an unbridged zirconium or hafnium basedmetallocene compound containing two cyclopentadienyl groups, two indenylgroups, or a cyclopentadienyl and an indenyl group.

Embodiment 42

The composition defined in any one of embodiments 33-40, whereincatalyst component I comprises an unbridged zirconium or hafnium basedmetallocene compound containing two cyclopentadienyl groups.

Embodiment 43

The composition defined in any one of embodiments 33-40, whereincatalyst component I comprises an unbridged zirconium or hafnium basedmetallocene compound containing two indenyl groups.

Embodiment 44

The composition defined in any one of embodiments 33-40, whereincatalyst component I comprises an unbridged zirconium or hafnium basedmetallocene compound containing a cyclopentadienyl and an indenyl group.

Embodiment 45

The composition defined in any one of embodiments 33-40, whereincatalyst component I comprises a dinuclear unbridged metallocenecompound with an alkenyl linking group.

Embodiment 46

The composition defined in any one of embodiments 33-40, whereincatalyst component I comprises an unbridged metallocene compound havingformula (I):

wherein M is any Group IV transition metal disclosed herein, Cp^(A) andCp^(B) independently are any cyclopentadienyl or indenyl group disclosedherein, and each X independently is any monoanionic ligand disclosedherein.

Embodiment 47

The composition defined in any one of embodiments 33-46, wherein theactivator comprises an activator-support, an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, or anycombination thereof.

Embodiment 48

The composition defined in any one of embodiments 33-47, wherein theactivator comprises an activator-support, the activator-supportcomprising any solid oxide treated with any electron-withdrawing aniondisclosed herein.

Embodiment 49

The composition defined in any one of embodiments 33-48, wherein theactivator comprises fluorided alumina, chlorided alumina, bromidedalumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, or any combination thereof.

Embodiment 50

The composition defined in any one of embodiments 33-48, wherein theactivator comprises a fluorided solid oxide and/or a sulfated solidoxide.

Embodiment 51

The composition defined in any one of embodiments 33-47, wherein theactivator comprises an aluminoxane compound.

Embodiment 52

The composition defined in any one of embodiments 33-51, wherein thecatalyst composition comprises a co-catalyst, e.g., any co-catalystdisclosed herein.

Embodiment 53

The composition defined in any one of embodiments 33-52, wherein theco-catalyst comprises any organoaluminum compound disclosed herein.

Embodiment 54

The composition defined in any one of embodiments 33-53, wherein aweight ratio of catalyst component I to catalyst component II in thecatalyst composition is in any range disclosed herein, e.g., from about10:1 to about 1:10, from about 5:1 to about 1:5, from about 2:1 to about1:2, etc.

Embodiment 55

The composition defined in any one of embodiments 33-54, wherein thecatalyst composition further comprises catalyst component III comprisingany half-metallocene compound disclosed herein.

Embodiment 56

The composition defined in embodiment 55, wherein catalyst component IIIcomprises a half-metallocene compound having formula (IIIA)

wherein Ind is any indenyl group disclosed herein, and each Xindependently is any monoanionic ligand disclosed herein.

Embodiment 57

The composition defined in embodiment 55, wherein catalyst component IIIcomprises a half-metallocene compound having formula (IIIB):Cr(Cp^(C))(X)(X)(L)_(n)  (IIIB);wherein Cp^(C) is any cyclopentadienyl, indenyl, or fluorenyl groupdisclosed herein, each X independently is any monoanionic liganddisclosed herein, each L is any neutral ligand disclosed herein, andinteger n is 0, 1 or 2.

Embodiment 58

The composition defined in any one of embodiments 55-57, wherein theweight percentage of catalyst component III is in any range disclosedherein, e.g., from about 5 to about 50%, from about 10 to about 45%,etc., based on the total weight of catalyst components I, II, and III.

Embodiment 59

An olefin polymerization process, the process comprising contacting thecatalyst composition defined in any one of embodiments 33-58 with anolefin monomer and optionally an olefin comonomer in a polymerizationreactor system under polymerization conditions to produce an olefinpolymer.

Embodiment 60

The process defined in embodiment 59, wherein the polymerization reactorsystem comprises a batch reactor, a slurry reactor, a gas-phase reactor,a solution reactor, a high pressure reactor, a tubular reactor, anautoclave reactor, or a combination thereof.

Embodiment 61

The process defined in any one of embodiments 59-60, wherein thepolymerization reactor system comprises a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.

Embodiment 62

The process defined in any one of embodiments 59-61, wherein thepolymerization reactor system comprises a loop slurry reactor.

Embodiment 63

The process defined in any one of embodiments 59-62, wherein thepolymerization reactor system comprises a single reactor.

Embodiment 64

The process defined in any one of embodiments 59-62, wherein thepolymerization reactor system comprises 2 reactors.

Embodiment 65

The process defined in any one of embodiments 59-62, wherein thepolymerization reactor system comprises more than 2 reactors.

Embodiment 66

The process defined in any one of embodiments 59-65, wherein the olefinmonomer comprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀olefin.

Embodiment 67

The process defined in any one of embodiments 59-66, wherein the olefinmonomer and the optional olefin comonomer independently comprise aC₂-C₂₀ alpha-olefin.

Embodiment 68

The process defined in any one of embodiments 59-67, wherein the olefinmonomer comprises ethylene.

Embodiment 69

The process defined in any one of embodiments 59-68, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising a C₃-C₁₀ alpha-olefin.

Embodiment 70

The process defined in any one of embodiments 59-69, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Embodiment 71

The process defined in any one of embodiments 59-70, wherein the olefinpolymer produced is defined in any one of embodiments 1-30.

Embodiment 72

An olefin polymer produced by the process defined in any one ofembodiments 59-70.

Embodiment 73

An ethylene polymer defined in any one of embodiments 1-30 produced bythe process defined in any one of embodiments 59-70.

Embodiment 74

An article comprising the polymer defined in embodiment 72 or 73.

Embodiment 75

A method or forming or preparing an article of manufacture comprising apolymer, the method comprising (i) performing the olefin polymerizationprocess defined in any one of embodiments 59-70 to produce the polymerdefined in any one of embodiments 1-30, and (ii) forming the article ofmanufacture comprising the polymer, e.g., utilizing any techniquedisclosed herein.

The invention claimed is:
 1. A catalyst composition comprising: catalyst component I comprising an unbridged Group IV transition metal based metallocene compound; catalyst component II comprising a bridged Group IV transition metal based metallocene compound with a fluorenyl group; catalyst component III comprising a half-metallocene compound having formula (IIIA):

 wherein: Ind is an indenyl group; and each X independently is a monoanionic ligand; an activator; and optionally, a co-catalyst.
 2. The composition of claim 1, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.
 3. An olefin polymerization process, the process comprising contacting a catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition comprises: an unbridged metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; a bridged metallocene compound with a cyclopentadienyl group and fluorenyl group, and an alkenyl substituent on the cyclopentadienyl group and/or on the bridging group; a half-metallocene compound having formula (IIIA):

 wherein: Ind is an indenyl group; and each X independently is a monoanionic ligand; an activator-support comprising a solid oxide treated with an electron-withdrawing anion; and an organoaluminum compound.
 4. The process of claim 3, wherein: the activator-support comprises a fluorided solid oxide and/or a sulfated solid oxide; the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof; catalyst component I comprises an unbridged metallocene compound having formula (I) and catalyst component II comprises a bridged metallocene compound having formula (II):

each M independently is Zr or Hf; Cp^(A) and Cp^(B) independently are a cyclopentadienyl or indenyl group; Cp is a cyclopentadienyl group; each X independently is a monoanionic ligand; R^(X) and R^(Y) independently are H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group; and E is a bridging group.
 5. The process of claim 3, wherein the polymerization reactor system comprises a slurry reactor, gas-phase reactor, solution reactor, or a combination thereof.
 6. The process of claim 3, wherein the catalyst composition is contacted with ethylene and an olefin comonomer comprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.
 7. The composition of claim 1, wherein: the catalyst composition comprises a co-catalyst; catalyst component I comprises an unbridged zirconium based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or a cyclopentadienyl and an indenyl group; and catalyst component II comprises a bridged zirconium or hafnium based metallocene compound with a cyclopentadienyl group and a fluorenyl group.
 8. The composition of claim 7, wherein: a weight ratio of catalyst component I to catalyst component II is from about 10:1 to about 1:10; and a weight percentage of catalyst component III is in a range from about 5 to about 50 wt. %, based on the total weight of catalyst components I, II, and III.
 9. The composition of claim 8, wherein: Ind is an unsubstituted indenyl group or a mono-substituted indenyl group; and each X is Cl.
 10. The composition of claim 7, wherein: a weight ratio of catalyst component I to catalyst component II is from about 5:1 to about 1:5; and a weight percentage of catalyst component III is in a range from about 10 to about 45 wt. %, based on the total weight of catalyst components I, II, and III.
 11. The composition of claim 7, wherein the activator comprises an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.
 12. The composition of claim 7, wherein: the activator comprises a fluorided solid oxide and/or a sulfated solid oxide; and the co-catalyst comprises an organoaluminum compound.
 13. The composition of claim 12, wherein the organoaluminum compound comprises trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, or any combination thereof.
 14. The process of claim 6, wherein catalyst component I comprises an unbridged zirconium based metallocene compound containing two indenyl groups.
 15. The process of claim 6, wherein catalyst component I comprises an unbridged zirconium based metallocene compound containing a cyclopentadienyl and an indenyl group.
 16. The process of claim 6, wherein each X is Cl.
 17. The composition of claim 1, wherein catalyst component I comprises an unbridged metallocene compound having formula (I) and catalyst component II comprises a bridged metallocene compound having formula (II):

each M independently is Zr or Hf; Cp^(A) and Cp^(B) independently are a cyclopentadienyl or indenyl group; Cp is a cyclopentadienyl group; each X independently is a monoanionic ligand; R^(X) and R^(Y) independently are H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆ hydrocarbylsilyl group; and E is a bridging group.
 18. The composition of claim 7, wherein: the activator comprises a fluorided solid oxide and/or a sulfated solid oxide; and the co-catalyst comprises an organoaluminum compound.
 19. The composition of claim 18, wherein a weight ratio of catalyst component I to catalyst component II is from about 2:1 to about 1:2.
 20. The composition of claim 18, wherein Ind is an unsubstituted indenyl group or a mono-substituted indenyl group. 